"IODOPHENYL-SUBSTITUTED CYCLIC KETOENOLS"

Abstract

The invention relates to novel iodophenyl-substituted cyclic ketenols of the formula (I)in which CKE, J, X and Y are as defined above, to a plurality of processes and intermediates for their preparation and to their use as pesticides and/or herbicides, and also to selective herbicidal ompositions comprising firstly iodophenyl-substituted cyclic of the formula (I) and secondly at least one crop plant compatibility-improving compound.

n8, for example, accordn8 to process (D) chlorocarbonyl 2-[(2,6-dmethyl-4-odophenyl)]
ketene and acetone as startn8 materals, the corse of the process accordn8 to the nventon
be represented by the reacton scheme below:

sn8, for example, accordn8 to process (E) chlorocarbonyl 2-(2,6-dmethyl-4-odophenyl) ketene
and thobenzamde as startn8 materals, the corse of the process accordn8 to the nventon can
be represented by the reacton scheme below:

sn8, for example, accordn8 to process (F) ethyl 5-(2,6-dmethyl-4-odophenyl)-2,3-
trmethylene-4-oxovalerate, the corse of the process accordn8 to the nventon can be

oxohexanoate, the corse of the process accordn8 to the nventon can be represented by the
reacton scheme below:

sn8, for example, accordn8 to process (Ha) hexahydropyrdazne and chlorocarbonyl 2
dmethyl-4-odo)phenyl] ketene as startn8 materals, the corse of the reacton of the process
accordn8 to the nventon can be represented by the reacton scheme below:
n8, for example, accordn8 to process (Hp) hexahydropyrdazne and dmethyl 2-(2,6-dmethyl-
4-odo)phenylmalonate as startn8 materals, the corse of the process accordn8 to the nventon
can be represented by the reacton scheme below:
sn8, for example, accordn8 to process (B) 3-(2,6-dmethyl-4-odophenyl)-5,5-
dmethylpyrroldne-2,4-done and acetc anhydrde as startn8 materals, the corse of the process
accordn8 to the nventon can be represented by the reacton scheme below:
sn8, for example, accordn8 to process (2) 8-[(2,6-dmethyl-4-odo)phenyl]-l-azabcyclo-
(4.3.()l'6)-nonane-7,9-done and ethyl chloroformate as startn8 materals, the corse of the process
accordn8 to the nventon can be represented by the reacton scheme below:
sn8, for example, accordn8 to process (K) 3-(2,6-dmethyl-4-odophenyl)-4-hydroxy-5-methyl-
6-(3-pyrdyl)pyrone and methyl chloromonothoformate as startn8 materals, the corse of the
reacton can be represented as follows:
sn8, for example, accordn8 to process (L) 3-(2,6-dmethyl-4-odophenyl)-5,5-pentamethylenepyrroldne-
2,4-done and methaneslfonyl chlorde as startn8 materal, the corse of
the reacton can be represented by the reacton scheme below:
sn8, for example, accordn8 to process (M) 3-(2,6-dmethyl-4-odophenyl)-4-hydroxy-5,5-dmethylpyrroldne-
2,4-done and 2,2,2-trfloroethyl methanethophosphonyl chlorde as startn8
materals, the corse of the reacton can be represented by the reacton scheme below:
(Figure Removed)
sn8, for example, accordn8 to process (N) 3-(2-ethyl-4-odo-6-methylphenyl]-5-cyclopropyl-5-
methylpyrroldne-2,4-done and NaOH as components, the corse of the process accordn8 to the
nventon can be represented by the reacton scheme below:
sn8, for example, accordn8 to process (O) varant a 3-(2,6-dmethyl-4-odophenyl)-4-hydroxy-
5,5-tetramethylene-A--dhydrofran-2-one and ethyl socyanate as startn8 materals, the corse of
the reacton can be represented by the reacton scheme below:
sn8, for example, accordn8 to process (O) varant 6 3-(2-methyl-4-odo-6-ethylphenyl)-5-
methylpyrroldne-2,4-done and dmethylcarbamoyl chlorde as startn8 materals, the corse of
the reacton can be represented by the scheme below:
(Figure Removed)
sn8, for example, accordn8 to process (P) 3-(4-bromo-2,6-dmethylphenyl)-5,5-dmethylpyrroldne-
2,4-done and sodm methoxde as startn8 materals, the corse of the reacton can be
represented by the scheme below:
The componds, rered as startn8 materals for the process (a) accordn8 to the nventon, of
checker: Above, please chan8e T to T
n whch
A, B, D, 2, X, Y and R8 are as defned above
are novel.
The acylamno acd esters of the formla () are obtaned, for example, when amno acd
dervatves of the formla (XX)
A, B, R8 and D are as defned above
are acylated wth sbsttted phenylacetc acd dervatves formla (XXFV)
2, X and Y are as defned above and
Z represents a leavn8 8rop ntrodced by rea8ents, sch as carbonyldmdazole,
carbonyldmdes (sch as, for example, dcyclohexylcarbondmde), phosphorylatn8
a8ents (sch as, for example, POC3, BOP-C), halo8enatn8 a8ents, for example thonyl
chlorde, oxalyl chlorde, phos8ene or chloroformc esters, for actvatn8 carboxylc acds
(Chem. Revews 52, 237-46 (953); Bhattacharya, ndan 2. Chem. 6, 34-5, 968)
or when acylamno acds of the formla (XXV)
A, B, D, 2, X and Y are as defned above
are esterfed (Chem. nd. (London) 568 (968)).
The componds of the formla (XXV) .
A, B, D, 2, X and Y are as defned above
are novel.
The componds of the formla (XXV) are obtaned when amno acds of the formla (XXV)
(Figure Removed)

A, B and D are as defned above
are acylated wth sbsttted phenylacetc acd dervatves of the formla (XXV)
2, X and Y are as defned above and
Z s as defned above,
for example accordn8 to Schotten-Bamann (Or8ankm, VEB Detscher Verla8 der Wssenschaften,
Berln 977, p. 505).
The componds of the formla (XXV) are novel. They can be prepared by processes known n
prncple and as llstrated n the examples (see, for example, H. Henecka, Hoben-Weyl,
Methoden der Or8anschen Cheme [Methods of Or8anc Chemstry], Vol. 8, pp. 467-469 (952)).
The componds of the formla (XXV) are obtaned, for example, by reactn8 sbsttted

wth halo8enatn8 a8ents (for example thonyl chlorde, thonyl bromde, oxalyl chlorde,
phos8ene, phosphors trchlorde, phosphors trbromde or phosphors pentachlorde),
phosphonylatn8 a8ents, sch as (for example POC, BOP-C), carbonyldmdazole,
carbonyldmdes (for example dcyclohexylcarbonyldmde), f approprate n the presence of a
dlent (for example optonally chlornated alphatc or aromatc hydrocarbons, sch as tolene or
methylene chlorde, or ethers, for example tetrahydrofran, doxane, methyl tert-btyl ether) at
temperatres of from -20°C to 50°C, preferably from -0°C to 00°C.
Some of the componds of the formlae (XX) and (XXV) are known, and/or they can be
prepared by known processes (see, for example, Compa8non, Moce Ann. Chm. (Pars) [4]
The sbsttted cyclc amnocarboxylc acds of the formla (XXV) n whch A and B form a rn8
are 8enerally obtanable by the Bcherer-Ber8s synthess or by the Strecker synthess, where they
are obtaned n dfferent somerc forms. Ths, the condtons of the Bcherer-Ber8s synthess
afford predomnantly the somers (herenbelow for the sake of smplcty referred to as p) n whch
the radcals R and the carboxyl 8rop are n eatoral postons, whereas the condtons of the
Strecker synthess afford predomnantly the somers (herenbelow for the sake of smpcty
referred to as a) n whch the amno 8rop and the radcals R are n eatoral postons.
Bcherer-Ber8s synthess Strecker synthess
(B somer) (a somer)
(L. Mnday, 2. Chem. Soc. 4372 (96); 2.T. Eward, C. 2tran8er, Can. 2. Chem. 53, 3339 sed n the above process (A), of the formla ()
A, B, D, 2, X, Y and R8 are as defned above
can frthermore be prepared by reactn8 amnontrles of the formla (XXV)
(Figure Removed)
A, B and D are as defned above
wth sbsttted phenylacetc acd dervatves of the formla (XXV)
(Figure Removed)
A, B, D, 2, X and Y are as defned above
and then sb2ectn8 these to an acdc alcoholyss.
The componds of the formla (XXX) are lkewse novel.
The componds, rered as startn8 materals n the process (B) accordn8 to the nventon, of
They can be prepared by methods known n prncple.
Ths, the componds of the formla () are obtaned, for example, when
2-hydroxycarboxylc esters of the formla (XXX-A)
A, B and R are as defned above
are acylated wth sbsttted phenylacetc acd dervatves of the formla (XXV)
2, X, Y and Z are as defned above
(Chem. Revews 52, 237-46 (953)).
Frthermore, componds of the formla () are obtaned when
sbsttted phenylacetc acds of the formla (XXV)
2, X and Y are as defned above
are alkylated wth a-halocarboxylc esters of the formla (XXX-B)
A, B and R8 are as defned above and
Hal represents chlorne or bromne.
Some of the componds of the formla (XXV) are commercally avalable, some are known;
however, some are also novel.
The componds of the formla (XXX-B) are commercally avalable.
The componds of the formla (XXV)
2, X and Y are as defned above
are obtaned, for example, when phenylacetc esters of the formla (XXX)
(Figure Removed)
2, X, Y and R8 are as defned above
are hydrolyzed n the presence of acds or bases, n the presence of a solvent nder 8enerally
known standard condtons.
Some of the componds of the formla (XXX) are commercally avalable, some are known, for
example from WO 0/7973; however, some are also novel.
The componds of the formla (XXX)
2, X, Y and R are as defned above
are frthermore obtaned by the process () descrbed n the examples
when phenylacetc esters of the formla (XXX-a)
R8, X and Y are as defned above
are reacted n the presence of oddes (preferably sodm odde or potassm odde) n the
presence of a base and, f approprate, n the presence of a catalyst (preferably copper salts, sch
as, for example, copper() odde).
The phenylacetc esters of the formla (XXX-a) are known n prncple, for example from the
applcatons WO 96/35 664, WO 97/02243, WO 97/0535, WO 98/05638 and DE-A-0 30 and they can be prepared by the processes descrbed n these pblcatons.
The componds, rered as startn8 materals for the process (C) above, of the formla (FV)
A, B, 2, V, X, Y and R8 are as defned above
are novel.
They can be prepared by methods known n prncple.
The componds of the formla (FV) are obtaned, for example, when
sbsttted phenylacetc esters of the formla (XXX)
2, X, Y and R8 are as defned above
are acylated wth 2-benzylthocarbonyl haldes of the formla (XXX)
A, B and V are as defned above and
Hal represents halo8en (n partclar chlorne or bromne)
n the presence of stron8 bases (see, for example, M.S. Chambers, E.2. Thomas, D.2. Wllams, 2.
Chem. Soc. Chem. Commn., (987), 228).
Some of the benzylthocarbonyl haldes of the formla (XXX) are known, and/or they can prepared by known processes (2. Antbotcs (983), 26, 589).
The halocarbonyl ketenes of the formla (V) rered as startn8 materals for the above (D), (E) and (H-ot) are novel. They can be prepared by methods known n prncple (cf., for
example, Or8. Prep. Proced. nt., 7, (4), 55-58, 975 and DE 945 703). Ths, for example,
are reacted wth acd haldes, sch as, for example, thonyl chlorde, phosphors(V) chlorde,
phosphors() chlorde, oxalyl chlorde, phos8ene or thonyl bromde, f approprate n the
presence of catalysts, sch as, for example, dmethylformamde, methylsterylformamde or
trphenylphosphne, and, f approprate, n the presence of bases, sch as, for example, pyrdne or
trethylamne.
Some of the sbsttted phenylmalonc acds of the formla (XXX) are known or commercally
avalable; however, some are also novel. They can be prepared n a smple manner by known
processes (cf., for example, Or8ankm, VEB Detscher Verla8 der Wssenschaften, Berln 977,
p. 57 ff, EP-A-528 56, WO 96/35 664, WO 97/02 243, WO 97/0535, WO 97/36868 and WO
98/05638).
Ths, phenylmalonc acds of the formla (XXX)
2, X and Y are as defned above
are obtaned when phenylmalonc esters of the formla (X)
(Figure Removed)
are ntally hydrolyzed n the presence of a base and of a solvent and then careflly acdfed for example, EP-A-528 56, WO 96/35 664, WO 97/02 243).
The malonc esters of the formla (X)
2, X and Y are as defned above
and represents OR8 or NH2,
where R8 s as defned above,
are known (for example WO 0/07973, Larock et al., Tetrahedron 52 2743 ff. (996); however,
some are also novel.
They can be prepared by 8enerally known methods of or8anc chemstry (cf., for example,
Tetrahedron Lett. 27, 2763 (986), Or8ankm VEB Detscher Verla8 der Wssenschaften, Berln
977, p. 587 ff., WO 96/35664, WO 97/02243, WO 97/0535, WO 97/36868, WO 98/05638 and
WO 99/47525).
The carbonyl componds, rered as startn8 materals for the process (D) accordn8 to the
nventon, of the formla (V)
or slylenol ethers thereof of the formla (Va)
A, D and R8 are as defned above
are commercally avalable componds, 8enerally known componds or componds whch can be
obtaned by known processes.
The preparaton of the ketene acd chlordes of the formla (V) rered as startn8 materals for
carryn8 ot the process (E) accordn8 to the nventon have already been descrbed above. The
thoamdes, rered for carryn8 ot the process (E) accordn8 to the nventon, of the formla

(Figure Removed)
in whichis as defined aboveare compounds which are enerally known in oranic chemistry.
The compounds, required as startin materials in the above process (F), of the formula (VIII)
(Figure Removed)

in whichThey can be prepared by methods known in principle.
The 5-aryl-4-ketocarboxylic esters of the formula (VIII) are obtained, for example, when 5-aryl-ketocarboxylic acids of the formula (XXXIV)in which, X, Y, A, B, Q and Q2 are as defined aboveare esterified (cf, for example, Oranikum, 5th edition, Berlin, 977, pae 499) or alkylated (seePreparation Example).
The 5-aryl-4-ketocarboxylic acids of the formula (XXXIV)
(Figure Removed)

in whichA, B, , Q, Q2, X and Y are as defined above
are novel; however, they can be prepared by methods known in principle (WO 96/0 79,
WO 97/4667, WO 9/392).The 5-aryl-4-ketocarboxylic acids of the formula (XXXFV) are obtained, for example, when
2-phenyl-3-oxoadipic esters of the formula (XXXV)
in whichA, B, , Ql, Q2, X and Y are as defined above and
R. and R° represent alkyl (in particular C]-C-alkyl) and,
when the compound of the formula (XXXVII-a) is used, R represents hydroen,
are decarboxylated, if appropriate in the presence of a diluent and if appropriate in the presence of
a base or acid (cf., for example, Oranikum, 5th edition, Berlin, 977, pae 59 to 52, WO
96/079, WO 97/4667, WO 9/392).
The compounds of the formula (XXXV)
A, B, , Q, Q2, X, Y, R, R' are as defined above and,
when the compound of the formula (XXXVII-a) is used, R represents hydroen
are novel.The compounds of the formula (XXXV) are obtained, for example,
when dicarboxylic monoester chlorides of the formula (XXXVI),
A, B, Q!, Q2 and R are as defined above and
Hal represents chlorine or bromine
or carboxylic anhydrides of the formula (XXXVII-a)
A, B, Q! and Q2 are as defined above
are acylated with a phenylacetic ester of the formula (XXXI)
, X, Y and R' are as defined above
in the presence of a diluent and in the presence of a base (cf., for example, M.S. Chambers, E. .Thomas, D.. Williams, . Chem. Soc. Chem. Commun., (97), 22, cf. also the PreparationExamples).
Some of the compounds of the formulae (XXXVI) and (XXXVII-a) are known compounds oforanic chemistry, and/or they can be prepared in a simple manner by methods known in principle.The compounds, required as startin materials in the above process (), of the formula (IX)A, B, , Q3, Q4, Q5, Q6, X, Y and R are as defined above
are novel.They can be prepared by methods known in principle.
The 6-aryl-5-ketocarboxylic esters of the formula (IX) are obtained, for example, when 6-aryl-5-ketocarboxylic acids of the formula (XXXVIII)
are esterified (cf., for example, Oranikum, 5th edition, Berlin, 977, pae 499, WO
The 6-aryl-5-ketocarboxylic acids of the formula (XXXVIII)
A, B, , Q3, Q4, Q5, Q6, X and Y are as defined above
are novel. They can be prepared by methods known in principle (WO 99/43649, WO
substituted 2-phenyl-3-oxoheptanedioic esters of the formula (XXXIX)
A, B, , Q3, Q4, Q5, Q6, X and Y are as defined above and
R. and R' represent alkyl (preferably C-C-alkyl) and,
when the compound of the formula (XXXVII-b) is used, R represents hydroen,
are hydrolyzed and decarboxylated, if appropriate in the presence of a diluent and if appropriate inthe presence of a base or acid (cf., for example, Oranikum, 5th edition, Berlin, 977, paes to 52, WO 99/43649, WO 99/469).The compounds of the formula (XXXIX)A, B, , Q3, Q4, Q5, Q6, x, Y, R and R' are as defined aboveare novel and can be obtainedwhen dicarboxylic esters of the formula (XL)A, B, Q3, Q4, Q5, Q6 and R are as defined above
or carboxylic anhydrides of the formula (XXXVII-b)(XXXVII-b)in which A, B, Q3, Q4, Q5, Q6 are as defined aboveare condensed with a substituted phenylacetic ester of the formula (XXXI)
(Figure Removed)
, X, Yand R' are as defined abovein the presence of a diluent and in the presence of a base.
Some of the compounds of the formula (XL) are known, and/or they can be prepared by knownprocesses.Some of the hydrazines, required as startin materials for the process (H-a) and (H-B) accordin tothe invention, of the formula (X)A and D are as defined above
are known, and/or they can be prepared by methods known from the literature (cf., for example,Liebis Ann. Chem. 55, 6 (954); Reaktionen der oranischen Synthese [Reactions of OranicSynthesis], C. Ferri, paes 22, 53; eor Thieme Verla Stuttart, 97; Liebis Ann. Chem.
443. 242 (925); Chem. Ber. 9, 255 (965), EP-A-50 26, WO 92/650, WO 99/47 525,
The compounds, required for the process (H-y) accordin to the invention, of the formula
in whichA, D, , X, Y and R are as defined above
are novel.The acylcarbazates of the formula (XII) are obtained, for example, when carbazates of the (Figure Removed)

A, R. and D are as defined aboveare acylated with substituted phenylacetic acid derivatives of the formula (XXFV), X, Y and Z are as defined above(Chem. Reviews 52, 237-46 (953); Bhattacharya, Indian . Chem. 6, 34-5, 96).Some of the carbazates of the formula (XLI) are commercially available compounds and, or they can be prepared by processes of oranic chemistry known in principle.The compounds of the formula (XXFV) have already been described in connection with theintermediates for the process (A) and (B).The acid halides of the formula (XIII), carboxylic anhydrides of the formula (XIV), chloroformic
esters or chloroformic thioesters of the formula (XV), chloromonothioformic esters or
chlorodithioformic esters of the formula (XVI), sulfonyl chlorides of the formula (XVII),
phosphorus compounds of the formula (XVIII) and metal hydroxides, metal alkoxides or amines ofthe formulae (XIX) and (XX) and isocyanates of the formula (XXI) and carbamoyl chlorides of theformula (XXII) furthermore required as startin materials for carryin out the processes (I), (K), (L), (M), (N) and (O) accordin to the invention are enerally known compounds of oranicor inoranic chemistry.
In addition, the compounds of the formulae (V), (VII), (XIII) to (XXII), (XXIII), (XXVI),
(XXVIII), (XXX-A), (XXX-B), (XXXII), (XXXVI), (XXXVII-a), (XXXVII-b), (XL) and are furthermore known from the patent applications cited at the outset, and/or they can be preparedby the methods stated in these publications.
The process (A) is characterized in that compounds of the formula (II) in which A, B, D, , and R° are as defined above are subected to an intramolecular condensation in the presence
Suitable for use as diluents in the process (A) accordin to the invention are all inert oranic
solvents. Preference is iven to usin hydrocarbons, such as toluene and xylene, furthermore
ethers, such as dibutyl ether, tetrahydrofuran, dioxane, lycol dimethyl ether and dilycol dimethylether, moreover polar solvents, such as dimethyl sulfoxide, sulfolane, dimethylformamide N-methylpyrrolidone, and also alcohols, such as methanol, ethanol, propanol, isopropanol, butanol,isobutanol and tert-butanol.
Suitable bases (deprotonatin aents) for carryin out the process (A) accordin to the invention
are all customary proton acceptors. Preference is iven to usin alkali metal and alkaline earth
metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide,
I manesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate,which can also be used in the presence of phase-transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adoen 464 (=
methyltrialkyl(C-C]o)ammonium chloride) or TDA (= tris(methoxyethoxyethyl)amine). It furthermore possible to use alkali metals, such as sodium or potassium. It is also possible to
i employ alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodiumhydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodiummethoxide, sodium ethoxide and potassium tert-butoxide.
When carryin out the process (A) accordin to the invention, the reaction temperatures can varied within a relatively wide rane. In eneral, the process is carried out at temperatures between20 0°C and 250°C, preferably between 50°C and 50°C.
The process (A) accordin to the invention is enerally carried out under atmospheric pressure.
When carryin out the process (A) accordin to the invention, the reaction components of the
formula (II) and the deprotonatin bases are enerally employed in approximately doubly
equimolar amounts. However, it is also possible to use a relatively lare excess (up to 3 mol) 25 one or the other component.The process (B) is characterized in that compounds of the formula (III) in which A, B, , X, Y andR. are as defined above are subected to an intramolecular condensation in the presence of adiluent and in the presence of a base.
Suitable for use as diluents in the process (B) accordin to the invention are all inert oranic
30 solvents. Preference is iven to usin hydrocarbons, such as toluene and xylene, furthermore
ethers, such as dibutyl ether, tetrahydrofuran, dioxane, lycol dimethyl ether and dilycol dimethylether, moreover polar solvents, such as dimethyl sulfoxide, sulfolane, dimethylformamide and
N-methylpyrrolidone, and also alcohols, such as methanol, ethanol, propanol, isopropanol, butanol,isobutanol and tert-butanol.
Suitable bases (deprotonatin aents) for carryin out the process (B) accordin to the invention
are all customary proton acceptors. Preference is iven to usin alkali metal and alkaline earth
metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide,
manesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate,
which can also be used in the presence of phase-transfer catalysts, such as, for example,
triethylbenzylammonium chloride, tetrabutylammonium bromide, Adoen 464 (=
methyltrialkyl(C-Ci0)ammonium chloride) or TDA (= tris(methoxyethoxyethyl)amine). It is
furthermore possible to use alkali metals, such as sodium or potassium. It is also possible to
employ alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium
hydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium
methoxide, sodium ethoxide and potassium tert-butoxide.
When carryin out the process (B) accordin to the invention, the reaction temperatures can be
varied within a relatively wide rane. In eneral, the process is carried out at temperatures between
The process (B) accordin to the invention is enerally carried out under atmospheric pressure.
When carryin out the process (B) accordin to the invention, the reaction components of the
formula (II) and the deprotonatin bases are enerally employed in approximately equimolar
amounts. However, it is also possible to use a relatively lare excess (up to 3 mol) of one or the
other component.The process (C) is characterized in that compounds of the formula (IV) in which A, B, V, , X, Yand R. are as defined above are cyclized intramolecularly in the presence of an acid and, ifappropriate, in the presence of a diluent.
Suitable diluents for the process (C) accordin to the invention are all inert oranic solvents.
Preference is iven to usin hydrocarbons, such as toluene and xylene, furthermore haloenated
hydrocarbons, such as dichloromethane, chloroform, ethylene chloride, chlorobenzene, dichlorobenzene,moreover polar solvents, such as dimethyl sulfoxide, sulfolane, dimethylformamide andN-methylpyrrolidone. It is furthermore possible to use alcohols, such as methanol, ethanol,propanol, isopropanol, butanol, isobutanol, tert-butanol.
If appropriate, the acid used may also serve as diluent.Suitable for use as acid in the process (C) accordin to the invention are all customary inoranicand oranic acids, such as, for example, hydrohalic acids, sulfuric acid, alkyl-, aryl- andhaloalkylsulfonic acids, in particular haloenated alkylcarboxylic acids, such as, for example,trifluoroacetic acid.
When carryin out the process (C) accordin to the invention, the reaction temperatures can be
varied within a relatively wide rane. In eneral, the process is carried out at temperatures between°C and 250°C, preferably between 50°C and 50°C.
The process (C) accordin to the invention is enerally carried out under atmospheric pressure.
When carryin out the process (C) accordin to the invention, the reaction components of the
formula (IV) and the acid are, for example, employed in equimolar amounts. However, it is alsopossible, if appropriate, to use the acid as solvent or as catalyst.
The process (D) accordin to the invention is characterized in that carbonyl compounds of the
formula (V) or their enole ethers of the formula (V-a) are reacted with ketene acid halides of theformula (VI) in the presence of a diluent and, if appropriate, in the presence of an acid acceptor.Suitable diluents for use in the process (D) accordin to the invention are all inert oranic solvents.Preference is iven to usin optionally haloenated hydrocarbons, such as toluene, xylene,mesitylene, chlorobenzene and dichlorobenzene, furthermore ethers, such as dibutyl ether, lycoldimethyl ether dilycol dimethyl ether and diphenyl ether, moreover polar solvents, such asdimethyl sulfoxide, sulfolane, dimethylformamide orN-methylpyrrolidone.
Suitable acid acceptors for carryin out the process variant (D) accordin to the invention are customary acid acceptors.Preference is iven to usin tertiary amines, such as triethylamine, pyridine, diazabicyclooctane
(DABCO), diazabicycloundecane (DBU), diazabicyclononene (DBN), Huni base and N,Ndimethylaniline.When carryin out the process variant (D) accordin to the invention, the reaction temperaturescan be varied within a relatively wide rane. Expediently, the process is carried out at temperaturesbetween 0°C and 250°C, preferably between 50°C and 220°C.
The process (D) accordin to the invention is expediently carried out under atmospheric pressure.When carryin out the process (D) accordin to the invention, the reaction components of theformulae (V) and (VI), in which A, D, , X and Y are as defined above and Hal represents haloen,and, if appropriate, the acid acceptors are enerally employed in approximately equimolaramounts. However, it is also possible to use a relatively lare excess (up to 5 mol) of onecomponent or the other.The process (E) accordin to the invention is characterized in that thioamides of the formula (VII)are reacted with ketene acid halides of the formula (VI) in the presence of a diluent and, if
appropriate, in the presence of an acid acceptor.
Suitable for use as diluents for the process variant (E) accordin to the invention are all inert
oranic solvents. Preference is iven to usin hydrocarbons, such as toluene and xylene,
furthermore ethers, such as dibutyl ether, lycol dimethyl ether and dilycol dimethyl ether,
moreover polar solvents, such as dimethyl sulfoxide, sulfolane, dimethylformamide and Nmethylpyrrolidone.Suitable for use as acid acceptors for carryin out the process (E) accordin to the invention are all
customary acid acceptors.
Preference is iven to usin tertiary amines, such as triethylamine, pyridine, diazabicyclooctane
(DABCO), diazabicycloundecane (DBU), diazabicyclononene (DBN), Hiini base and N,Ndimethylaniline.
When carryin out the process (E) accordin to the invention, the reaction temperatures can be
varied within a relatively wide rane. Expediently, the process is carried out at temperatures
between 0°C and 250°C, preferably between 20°C and 220°C.
The process (E) accordin to the invention is expediently carried out under atmospheric pressure.When carryin out the process (E) accordin to the invention, the reaction components of theformulae (VII) and (VI), in which A, , X and Y are as defined above and Hal represents haloen,and, if appropriate, the acid acceptors are enerally employed in approximately equimolaramounts. However, it is also possible to use a relatively lare excess (up to 5 mol) of onecomponent or the other.The process (F) is characterized in that compounds of the formula (VIII) in which A, B, , Q, Q,
X, Y and R are as defined above are subected to an intramolecular condensation in the presenceof abase.Suitable diluents for use in the process (F) accordin to the invention are all oranic solventswhich are inert toward the reaction participants. Preference is iven to usin hydrocarbons, toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, lycoldimethyl ether and dilycol dimethyl ether, moreover polar solvents, such as dimethyl sulfoxide,sulfolane, dimethylformamide and N-methylpyrrolidone. It is furthermore possible to use alcohols,such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol.Suitable bases (deprotonatin aents) for carryin out the process (F) accordin to the inventionare all customary proton acceptors. Preference is iven to usin alkali metal and alkaline earthmetal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide,manesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate,which can also be used in the presence of phase-transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adoen 464 (=methyltrialkyl(C-C]0)ammonium chloride) or TDA (= tris(methoxyethoxyethyl)amine). It isfurthermore possible to use alkali metals, such as sodium or potassium. It is also possible toemploy alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodiumhydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium
methoxide, sodium ethoxide and potassium tert-butoxide.
When carryin out the process (F) accordin to the invention, the reaction temperatures can be
varied within a relatively wide rane. In eneral, the process is carried out at temperatures between-75°C and 250°C, preferably between -50°C and 50°C.
The process (F) accordin to the invention is enerally carried out under atmospheric pressure.
When carryin out the process (F) accordin to the invention, the reaction components of the
formula (VIII) and the deprotonatin bases are enerally employed in approximately equimolar
amounts. However, it is also possible to use a relatively lare excess (up to 3 mol) of one or theother component.The process () is characterized in that compounds of the formula (IX) in which A, B, Q, Q,Q, Q6, , X, Y and R are as defined above are subected to an intramolecular condensation in presence of bases.Suitable diluents for use in the process () accordin to the invention are all oranic solventswhich are inert toward the reaction participants. Preference is iven to usin hydrocarbons, such astoluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, lycol
dimethyl ether and dilycol dimethyl ether, moreover polar solvents, such as dimethyl sulfoxide,
sulfolane, dimethylformamide and N-methylpyrrolidone. It is furthermore possible to use alcohols,
such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol.
Suitable bases (deprotonatin aents) for carryin out the process () accordin to the invention
are all customary proton acceptors.
Preference is iven to usin alkali metal and alkaline earth metal oxides, hydroxides and
carbonates, such as sodium hydroxide, potassium hydroxide, manesium oxide, calcium oxide,
sodium carbonate, potassium carbonate and calcium carbonate, which can also be used in the
presence of phase-transfer catalysts, such as, for example, triethylbenzylammonium chloride,
tetrabutylammonium bromide, Adoen 464 (= methyltrialkyl(C-C]0)ammonium chloride) TDA (= tris(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals, such assodium or potassium. It is also possible to employ alkali metal and alkaline earth metal amides andhydrides, such as sodium amide, sodium hydride and calcium hydride, and additionally also alkalimetal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.When carryin out the process () accordin to the invention, the reaction temperatures can bevaried within a relatively wide rane. In eneral, the process is carried out at temperatures between0°C and 250°C, preferably between 50°C and 50°C.
The process () accordin to the invention is enerally carried out under atmospheric pressure.
When carryin out the process () accordin to the invention, the reaction components of the
formula (IX) and the deprotonatin bases are enerally employed in approximately equimolar
amounts. However, it is also possible to use a relatively lare excess (up to 3 mol) of one or other component.The process (H-a) accordin to the invention is characterized in that hydrazines of the formula (X)or salts of these compounds are reacted with ketene acid halides of the formula (VI) in thepresence of a diluent and, if appropriate, in the presence of an acid acceptor.Suitable diluents for use in the process (H-a) accordin to the invention are all inert oranicsolvents. Preference is iven to usin optionally chlorinated hydrocarbons, such as, for example,mesitylene, chlorobenzene and dichlorobenzene, toluene, xylene, furthermore ethers, such asdibutyl ether, lycol dimethyl ether, dilycol dimethyl ether and diphenylethane, moreover polarsolvents, such as dimethyl sulfoxide, sulfolaiie, dimethylformamide or N-methylpyrrolidone.Suitable acid acceptors for carryin out the process variant (H-a) accordin to the invention Preference is iven to usin tertiary amines, such as triethylamine, pyridine, diazabicyclooctane(DABCO), diazabicycloundecane (DBU), diazabicyclononene (DBN), Hiini base and N,Ndimethylaniline.When carryin out the process variant (H-a) accordin to the invention, the reaction temperaturescan be varied within a relatively wide rane. Expediently, the process is carried out at temperatures
between 0°C and 250°C, preferably between 50°C and 220°C.
The process (H-a) accordin to the invention is expediently carried out under atmospheric
pressure.When carryin out the process (H-a) accordin to the invention, the reaction components of formulae (VI) and (X), in which A, D, , X and Y are as defined above and Hal represents haloen,and, if appropriate, the acid acceptors are enerally employed in approximately equimolaramounts. However, it is also possible to use a relatively lare excess (up to 5 mol) of onecomponent or the other.
The process (H-B) is characterized in that hydrazines of the formula (X) or salts of this compound,in which A and D are as defined above, are subected to a condensation with malonic esters ormalonamides of the formula (XI) in which U, , X, Y and R° are as defined above, in the presenceof a base.Suitable diluents for use in the process (H-B) accordin to the invention are all inert oranic
solvents. Preference is iven to usin optionally haloenated hydrocarbons, such as toluene,
xylene, mesitylene, chlorobenzene and dichlorobenzene, furthermore ethers, such as dibutyl ether,
tetrahydrofuran, dioxane, dipheny! ether, lycol dimethyl ether and dilycol dimethyl ether,
moreover polar solvents, such as dimethyl sulfoxide, sulfolane, dimethylformamide,
dimethylacetamide and N-methylpyrrolidone, and also alcohols, such as methanol, ethanol,
propanol, isopropanol, butanol, isobutanol and tert-butanol.
Suitable bases (deprotonatin aents) for carryin out the process (H-P) accordin to the invention
are all customary proton acceptors. Preference is iven to usin alkali metal and alkaline earth
metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide,
manesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate,
which can also be used in the presence of phase-transfer catalysts, such as, for example,
triethylbenzylammonium chloride, tetrabutylammonium bromide, Adoen 464 (=
methyltrialkyl(C-C]Q)ammoniurn chloride) or TDA (= tris(methoxyethoxyethyl)amine). It isfurthermore possible to use alkali metals, such as sodium or potassium. It is also possible to
employ alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodiumhydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodiummethoxide, sodium ethoxide and potassium tert-butoxide.
It is also possible to use tertiary amines, such as triethylamine, pyridine, diazabicyclooctane
(DABCO), diazabicycloundecane (DBU), diazabicyclononene (DBN), Hiini base and N,Ndimethylaniline.When carryin out the process (H-B) accordin to the invention, the reaction temperatures can bevaried within a relatively wide rane. In eneral, the process is carried out at temperatures between0°C and 20°C, preferably between 50°C and 0°C.
The process (H-B) accordin to the invention is enerally carried out under atmospheric pressure.When carryin out the process (H-3) accordin to the invention, the reaction components of theformulae (XI) and (X) are enerally employed in approximately equimolar amounts. However, it isalso possible to use a relatively lare excess (up to 3 mol) of one component or the other.The process (H-y) is characterized in that compounds of the formula (XII) in which A, D, , X, Yand R. are as defined above are subected to an intramolecular condensation in the presence Suitable for use as diluents in the process (H-y) accordin to the invention are all inert oranicolvents. Preference is iven to usin hydrocarbons, such as toluene and xylene, furthermoreethers, such as dibutyl ether, tetrahydrofuran, dioxane, lycol dimethyl ether and dilycol dimethylether, moreover polar solvents, such as dimethyl sulfoxide, sulfolane, dimethylformamide and
N-methylpyrrolidone, and also alcohols, such as methanol, ethanol, propanol, isopropanol, butanol,isobutanol and tert-butanol.
Suitable bases (deprotonatin aents) for carryin out the process (H-y) accordin to the invention
are all customary proton acceptors. Preference is iven to usin alkali metal and alkaline earth
metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide,
manesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate,which can also be used in the presence of phase-transfer catalysts, such as, for example,triethylbenzylammonium chloride, tetrabutylammonium bromide, Adoen 464 (=
methyltrialkyl(C-Ci0)ammoniurn chloride) or TDA (= tris(methoxyethoxyethyl)amine). It isfurthermore possible to use alkali metals, such as sodium or potassium. It is also possible to
employ alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodiumhydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodiummethoxide, sodium ethoxide and potassium tert-butoxide.
When carryin out the process (H-y) accordin to the invention, the reaction temperatures can bevaried within a relatively wide rane. In eneral, the process is carried out at temperatures between0°C and 250°C, preferably between 50°C and 50°C.
The process (H-y) accordin to the invention is enerally carried out under atmospheric pressure.When carryin out the process (H-y) accordin to the invention, the reaction components of formula (XII) and the deprotonatin bases are enerally employed in approximately doublyequimolar amounts. However, it is also possible to use a relatively lare excess (up to 3 mol) ofone or the other component.
The process (I-a) is characterized in that compounds of the formulae (I-l-a) to (I--a) are in eachcase reacted with carbonyl halides of the formula (XIII), if appropriate in the presence of a diluentand if appropriate in the presence of an acid binder.
Suitable diluents for use in the process (I-a) accordin to the invention are all solvents which areinert toward the acid halides. Preference is iven to usin hydrocarbons, such as benzine, benzene,toluene, ylene and tetralin, furthermore haloenated hydrocarbons, such as methylene chloride,chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, suchas acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuranand dioxane, additionally carboxylic esters, such as ethyl acetate, and also stronly polar solvents,such as dimethyl sulfoxide and sulfolane. The hydrolytic stability of the acid halide permittin, thereaction can also be carried out in the presence of water.
Suitable acid binders for the reaction accordin to the process (I-a) accordin to the invention areall customary acid acceptors. Preference is iven to usin tertiary amines, such as triethylamine,
pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene
(DBN), Hiini base and N,N-dimethylaniline, furthermore alkaline earth metal oxides, such manesium oxide and calcium oxide, moreover alkali metal and alkaline earth metal carbonates,
such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal
hydroxides, such as sodium hydroxide and potassium hydroxide.
The reaction temperatures in the process (I-a) accordin to the invention may be varied within arelatively wide rane. In eneral, the process is carried out at temperatures between -20°C and
+50°C, preferably between 0°C and 00°C.When carryin out the process (I-a) accordin to the invention, the startin materials of theformulae (I-l-a) to (I--a) and the carbonyl halide of the formula (XIII) are enerally eachemployed in approximately equivalent amounts. However, it is also possible to use a relatively
lare excess (up to 5 mol) of the carbonyl halide. Work-up is carried out by customary methods.The process (I-B) is characterized in that compounds of the formulae (I-l-a) to (I--a) are reactedwith carboxylic anhydrides of the formula (XFV), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid binder.
Suitable for use as diluents in the process (I-B) accordin to the invention are, preferably, thosediluents which are also preferred when acid halides are used. Besides, it is also possible for excess to act simultaneously as diluent.
Suitable acid binders for process (I-B), which are added, if appropriate, are preferably those acidbinders which are also preferred when acid halides are used.
The reaction temperatures in the process (I-B) accordin to the invention can be varied within
relatively wide rane. In eneral, the process is carried out at temperatures between -20°C and
+50°C, preferably between 0°C and 00°C.
When carryin out the process (I-B) accordin to the invention, the startin materials of the
formulae (I-l-a) to (I--a) and the carboxylic anhydride of the formula (XIV) are enerally each
employed in approximately equivalent amounts. However, it is also possible to use a relativelylare excess (up to 5 mol) of the carboxylic anhydride. Work-up is carried out by customarymethods.
In eneral, diluent and excess carboxylic anhydride and the carboxylic acid formed are removed by
distillation or by washin with an oranic solvent or with water.
The process () is characterized in that compounds of the formulae (I-l-a) to (I-a) are in each case
reacted with chloroformic esters or chloroformic thioesters of the formula (XV), if appropriate in
the presence of a diluent and if appropriate in the presence of an acid binder.
Suitable acid binders for the reaction accordin to process () accordin to the invention are all
customary acid acceptors. Preference is iven to usin tertiary amines, such as triethylamine,
pyridine, DABCO, DBU, DBA, Hiini base and N,N-dimethylaniline, furthermore alkaline earth
metal oxides, such as manesium oxide'and calcium oxide, moreover alkali metal and alkaline
earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and
also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
Suitable diluents for use in the process () accordin to the invention are all solvents which are
inert toward the chloroformic esters or chloroformic thioesters. Preference is iven to usin
hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin, furthermore haloenated
hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and odichlorobenzene,
moreover ketones, such as acetone and methyl isopropyl ketone, furthermore
ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as
ethyl acetate, and also stronly polar solvents, such as dimethyl sulfoxide and sulfolane.
When carryin out the process () accordin to the invention, the reaction temperatures can be
varied within a relatively wide rane, If the reaction is carried out in the presence of a diluent and
an acid binder, reaction temperatures are enerally between -20°C and +00°C, preferably between
0°C and 50°C.
The process () accordin to the invention is enerally carried out under atmospheric pressure.
When carryin out the process () accordin to the invention, the startin materials of the formulae
(I-l-a) to (I--a) and the appropriate chloroformic ester or chloroformic thioester of the formula
(XIII) are enerally each employed in approximately equivalent amounts. However, it is also
possible to use a relatively lare excess (up to 2 mol) of one component or the other. Work-up is
carried out by customary methods. In eneral, precipitated salts are removed and the reaction
mixture that remains is concentrated by removin the diluent under reduced pressure.
The process (K) accordin to the invention is characterized in that compounds of the formulae (I-
-a) to (I--a) are in each case reacted with compounds of the formula (XVI) in the presence of a
diluent and, if appropriate, in the presence of an acid binder.
In preparation process (K), about mol of chloromonothioformic ester or chlorodithioformic ester
of the formula (XVI) is reacted per mole of the startin material of the formulae (I-l-a) to (I--a) at
from 0 to 20°C, preferably from 20 to 60°C.
Suitable diluents, which are added, if appropriate, are all inert polar oranic solvents, such as
ethers, amides, sulfones, sulfoxides, and also haloenated alkanes.
Preference is iven to usin dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or methylene
chloride.
If, in a preferred embodiment, the enolate salt of the compounds (I-l-a) to (I--a) is prepared by
addition of stron deprotonatin aents, such as, for example, sodium hydride or potassium tertbutoxide,
the further addition of acid 20-
If acid binders are used, customary inoranic or oranic bases are suitable, by way of example
sodium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine.
The reaction can be carried out at atmospheric pressure or under elevated pressure and is
preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.
The process (L) accordin to the invention is characterized in that compounds of the formulae (--
a) to (I--a) are in each case reacted with sulfonyl chlorides of the formula (XVII), if appropriate
in the presence of a diluent and if appropriate in the presence of an acid binder.
In preparation process (L), about mol of sulfonyl chloride of the formula (XVII) is reacted per
mole of startin material of the formula (I-l-a to I--a), at from -20 to 50°C, preferably from 20 to
70°C.
Suitable diluents, which are added, if appropriate, are all inert polar oranic solvents, such as
ethers, amides, nitriles, sulfones, sulfoxides or haloenated hydrocarbons, such as methylene
chloride.
Preference is iven to usin dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, methylene
chloride.
If, in a preferred embodiment, the enolate salt of the compounds (I-l-a) to (I--a) is prepared by
addition of stron deprotonatin aents (such as, for example, sodium hydride or potassium tertbutoxide),
the further addition of acid binders may be dispensed with.
If acid binders are used, customary inoranic or oranic bases are suitable, by way of example
sodium hydroxide, sodium carbonate, potassium carbonate, pyridine, triethylamine.
The reaction can be carried out at atmospheric pressure or under elevated pressure and is
preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.
The process (M) accordin to the invention is characterized in that compounds of the formulae (I-
-a) to (I--a) are in each case reacted with phosphorus compounds of the formula (XVIII), if
appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
In preparation process (M), to obtain compounds of the formulae (I-l-e) to (I--e) to 2,
preferably to .3, mol of the phosphorus compound of the formula (XVIII) are employed per
mole of the compounds (I-l-e) to (I--e), at temperatures between -40°C and 50°C, preferably
between-0 and 0°C.
Suitable diluents which are added, if appropriate, are all inert polar oranic solvents, such as
ethers, amides, nitriles, alcohols, sulfides, sulfones, sulfoxides, etc.
Preference is iven to usin acetonitrile, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide,
methylene chloride.
Suitable acid binders, which are added, if appropriate, are customary inoranic or oranic bases,
such as hydroxides, carbonates or amines. Sodium hydroxide, sodium carbonate, potassium
carbonate, pyridine, triethylamine may be mentioned by way of example.
The reaction can be carried out at atmospheric pressure or under elevated pressure and is
preferably carried out at atmospheric pressure. Work-up is carried out by customary methods of
oranic chemistry. The end products obtained are preferably purified by crystallization,
chromatoraphic purification or by so-called "incipient distillation", i.e. removal of the volatile
components under reduced pressure.
The process (N) is characterized in that compounds of the formulae (I-l-a) to (I--a) are reacted
with metal hydroxides or metal alkoxides of the formula (XIX) or amines of the formula (XX), if
appropriate in the presence of a diluent.
Suitable for use as diluents in the process (N) accordin to the invention are, preferably, ethers,
such as tetrahydrofuran, dioxane, diethyl ether, or else alcohols, such as methanol, ethanol,
isopropanol, but also water.
The process (N) accordin to the invention is enerally carried out under atmospheric pressure.
The reaction temperatures are enerally between -20°C and 00°C, preferably between 0°C accordin to the invention is characterized in that compounds of the formulae (I-
-a) to (I--a) are in each case reacted with (O-a) compounds of the formula (XXI), if appropriate
in the presence of a diluent and if appropriate in the presence of a catalyst, or (O-I3) with
compounds of the formula (XXII), if appropriate in the presence of a diluent and if appropriate in
the presence of an acid binder.
In preparation process (O-a), about mol of isocyanate of the formula (XXI) is employed per
mole of startin material of the formulae (I-l-a) to (I--a), at from 0 to 00°C, preferably
Suitable diluents, which are added, if appropriate, are all inert oranic solvents, such as ethers,
amides, nitriles, sulfones, sulfoxides.
If appropriate, catalysts may be added to accelerate the reaction. Suitable for use as catalysts are,
very advantaeously, oranotin compounds, such as, for example, dibutyltin dilaurate. The
reaction is preferably carried out at atmospheric pressure.
In preparation process (O-B), about mol of carbamoyl chloride of the formula (XXII) is employed
per mole of startin material of the formulae (I-l-a) to (I--a) at from -20 to 50°C, preferably
from 0 to 70°C.
Suitable diluents, which are added, if appropriate, are all inert polar oranic solvents, such as
ethers, amides, sulfones, sulfoxides or haloenated hydrocarbons.
Preference is iven to usin dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or methylene
chloride.
If, in a preferred embodiment, the enolate salt of the compound (I-l-a) to (I--a) is prepared by
addition of stron deprotonatin aents (such as, for example, sodium hydride or potassium tertbutoxide),
the further addition of acid binders may be dispensed with.
If acid binders are used, customary inoranic or oranic bases are suitable, by way of example
sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.
The reaction may be carried out at atmospheric pressure or under elevated pressure and is
preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.
The process (Pa) is characterized in that compounds of the formulae (I-l-a) to (I--a) in which defined above and W preferably represents bromine are
reacted with metal iodides (for example sodium iodide, potassium iodide), if appropriate in the
presence of a base and a Cu(I) salt (for example CuBr or Cul).
Suitable for use as diluents in the process (Pa) accordin to the invention are all oranic solvents
which are inert toward the reaction participants. Preference is iven to usin hydrocarbons, such toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, lycol
dimethyl ether and dilycol dimethyl ether, moreover polar solvents, such as dimethyl sulfoxide,
sulfolane, dimethylformamide, dimethylacetamide and N-methylpyrrolidone, esters, such as methyl
acetate, ethyl acetate, propyl acetate, and also alcohols, such as, for example, methanol, ethanol,
propanol, isopropanol, butanol and isobutanol.
Suitable bases for carryin out the process (Pa) accordin to the invention are especially oranic
bases. Preference is iven to usin amines, such as, for example, N,N-dimethylethylenediamine, ,2-
diaminocyclohexane.
When carryin out the process (Pa) accordin to the invention, the reaction temperature can be
varied within a relatively wide rane. In eneral, the process is carried out at temperatures between
0°C and 250°C, preferably between 50°C and 50°C.
The process (Pa) accordin to the invention is enerally carried out under atmospheric pressure.
When carryin out the process (Pa) accordin to the invention, the reaction component of the
formula (I-l-a) to (I--a') is enerally reacted with excesses of the metal iodides of up to 20 mol,
preferably from . to 5 mol. The copper(I) salts are enerally employed in catalytic amounts; from
0.00 to 0.5 mol, preferably from 0.0 to 0.2 mol. However, they can also be employed in equimolar
amounts.
The process (Pli) is characterized in that compounds of the formulae (I-l-a) to (I--a) in which A, B,
s defined above and W preferably represents bromine are
subected to a haloen/metal exchane with metal oranyls and the anion formed is reacted with
iodinatin aents.
Suitable diluents for use in the process (PB) accordin to the invention are all oranic solvents which
are inert toward the reaction participants. Preference is iven to usin hydrocarbons, such as toluene
and xylene, furthermore ethers, such as diethyl ether, methyl tert-butyl ether, dibutyl ether,
tetrahydrofuran, dioxane, lycol dimethyl ether and dilycol dimethyl ether.
Suitable for use as iodinatin aents for carryin out the process (PB) are customary reaents, such as
iodine, iodine monochloride, iodine monobromide.
When carryin out the process (PB) accordin to the invention, all customary metal oranyls can be
used for the haloen/metal exchane. Preference is iven to usin n-butyllithium, sec-butyllithium,
tert-butyllithium, phenyllithium.
When carryin out the process (PB) accordin to the invention, the reaction temperature can be varied
within a relatively wide rane. In eneral, the process is carried out at temperatures between -20°C
and 50°C, preferably between -7°C and 30°C.
The process (PB) accordin to the invention is enerally carried out under atmospheric pressure.
When carryin out the process (PB) accordin to the invention, the reaction component of the formula
(I-l-a) to (I--a) is enerally reacted with excesses of the metal oranyls and the iodinatin aents of
up to 20 mol, preferably from .2 to 5 mol.
The inventive active compounds/active compound combinations, in combination with ood plant
tolerance and favourable toxicity to warm-blooded animals and bein tolerated well by the
environment, are suitable for protectin plants and plant orans, for increasin the harvest yields,
for improvin the quality of the harvested material and for controllin animal pests, in particular
insects, arachnids, helminths, nematodes and molluscs, which are encountered in ariculture, in
horticulture, in animal husbandry, in forests, in ardens and leisure facilities, in the protection of
stored products and of materials, and in the hyiene sector. They may be preferably employed as
plant protection aents. They are active aainst normally sensitive and resistant species and aainst
all or some staes of development. The abovementioned pests include:
From the order of the Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp.,
Linonathus spp., Pediculus spp., Trichodectes spp.
From the class of the Arachnida, for example, Acarus siro, Aceria sheldoni, Aculops spp., Aculus
spp., Amblyomma spp., Aras spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa,
Chorioptes spp., Dermanyssus allinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp.,
Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans,
Metatetranychus spp., Olionychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta
oleivora, Polyphaotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizolyphus spp.,
Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp.,
Vasates lycopersici.
From the class of the Bivalva, for example, Dreissena spp.
From the order of the Chilopoda, for example, eophilus spp., Scutiera spp.
From the order of the Coleoptera, for example, Acanthoscelides obtectus, Adoretus spp.,
Aelastica alni, Ariotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp.,
Anthonomus spp., Anthrenus spp., Apoonia spp., Atomaria spp., Attaenus spp., Bruchidius
obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites
spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica
spp., Epilachna spp., Faustinus cubae, ibbium psylloides, Heteronychus arator, Hylamorpha
eleans, Hylotrupes baulus, Hypera postica, Hypothenemus spp., Lachnosterna consanuinea,
Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meliethes aeneus,
Melolontha melolontha, Midolus spp., Monochamus spp., Naupactus xanthoraphus, Niptus
hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia
ucunda, Phaedon cochleariae, Phyllophaa spp., Popillia aponica, Premnotrypes spp., Psylliodes
chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp.,
Sphenophorus spp., Sternechus .spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trooderma
spp., Tychius spp., Xylotrechus spp., Zabrus spp.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Diplopoda, for example, Blaniulus uttulatus.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Bibio hortulanus,
Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia
anthropophaa, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp.,
Fannia spp., astrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp.,
Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Peomyia hyoscyami, Phorbia
spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa.
From the class of the astropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp.,
Deroceras spp., alba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
From the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum,
Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Bruia malayi,
Bruia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium
spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus
ranulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp.,
Heterakis spp., Hymenolepis nana, Hyostronulus spp., Loa Loa, Nematodirus spp.,
Oesophaostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertaia spp., Paraonimus
spp., Schistosomen spp, Stronyloides fuelleborni, Stronyloides stercoralis, Stronyloides spp.,
Taenia sainata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi,
Trichinella nelsoni, Trichinella pseudopsiralis, Trichostronulus spp., Trichuris trichuria,
Wuchereria bancrofti.
It is furthermore possible to control Protozoa, such as Eimeria.
From the order of the Heteroptera, for example, Anasa tristis, Antestiopsis spp., Blissus spp.,
Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus
piperis, Dichelops furcatus, Diconocoris hewerti, Dysdercus spp., Euschistus spp., Euryaster spp.,
Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptolossus phyllopus, Lyus spp.,
Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata,
Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlberella sinularis,
Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
From the order of the Homoptera, for example, Acyrthosipon spp., Aeneolamia spp., Aonoscena
spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui,
Aonidiella spp., Aphanostima piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus
spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp.,
Brevicoryne brassicae, Calliypona marinata, Carneocephala fulida, Ceratovacuna laniera,
Cercopidae, Ceroplastes spp., Chaetosiphon fraaefolii, Chionaspis tealensis, Chlorita onukii,
Chromaphis ulandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus
spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Drosicha
spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis
bilobatus, eococcus coffeae, Homalodisca coaulata, Hyalopterus arundinis, Icerya spp.,
Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp.,
Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella
spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia
ribisniri, Nephotettix spp., Nilaparvata luens, Oncometopia spp., Orthezia praelona,
Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphius spp., Pererinus maidis,
Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis
aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentaona,
Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada
ias, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis
raminum, Selenaspidus articulatus, Soata spp., Soatella furcifera, Soatodes spp., Stictocephala
festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp.,
Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp.,
Monomorium pharaonis, Vespa spp.
From the order of the Isopoda, for example, Armadillidium vulare, Oniscus asellus, Porcellio
scaber.
From the order of the Isoptera, for example, Reticulitermes spp.
From the order of the Lepidoptera, for example, Acronicta maor, Aedia leucomelas, Arotis spp.,
Alabama arillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus
piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo
spp., Choristoneura fumiferana, Clysia ambiuella, Cnaphalocerus spp., Earias insulana, Ephestia
kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., alleria mellonella, Helicoverpa spp.,
Heliothis spp., Hofmannophila pseudospretella, Homona mananima, Hyponomeuta padella, Laphyma
spp., Lithocolletis blancardella, Lithophane antennata, Loxarotis albicosta, Lymantria
spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp.,
Oulema oryzae, Panolis flammea, Pectinophora ossypiella, Phyllocnistis citrella, Pieris spp.,
Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis,
Spodoptera spp., Thermesia emmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana,
Trichoplusia spp.
From the order of the Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella
ermanica, ryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta
americana, Schistocerca rearia.
From the order of the Siphonaptera, for example, Ceratophyllus spp., Xenopsylla cheopis.
From the order of the Symphyla, for example, Scutierella immaculata.
From the order of the Thysanoptera, for example, Baliothrips biformis, Enneothrips flavens,
Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus,
Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
From the order of the Thysanura, for example, Lepisfna saccharina.
The phytoparasitic nematodes include, for example, Aphelenchoides spp., Bursaphelenchus spp.,
Dirylenchus dipsaci, lobodera spp., Heterodera spp., Lonidorus spp., Meloidoyne spp.,
Pratylenchus spp., Radopholus similis, Trichodorus spp., Tylenchulus semipenetrans, Xiphinema
spp.
If appropriate, the compounds/active compound combinations accordin to the invention can, at
certain concentrations or application rates, also be used as herbicides, safeners, rowth reulators
or aents to improve plant properties, or as microbicides, for example as funicides, antimycotics,
bactericides, viricides (includin aents aainst viroids) or as aents aainst MLO (Mycoplasmalike
oranisms) and RLO (Rickettsia-like oranisms). If appropriate, they can also be employed as
intermediates or precursors for the synthesis of other active compounds.
All plants and plant parts can be treated in accordance with the invention. Plants are to be
understood as meanin in the present context all plants and plant populations such as desired and
undesired wild plants or crop plants (includin naturally occurrin crop plants). Crop plants can be
plants which can be obtained by conventional plant breedin and optimization methods or by
biotechnoloical and enetic enineerin methods or by combinations of these methods, includin
the transenic plants and includin the plant cultivars protectable or not protectable by plant
breeders' rihts. Plant parts are to be understood as meanin all parts and orans of plants above
and below the round, such as shoot, leaf, flower and root, examples which may be mentioned
bein leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.
The plant parts also include harvested material, and veetative and enerative propaation
material, for example cuttins, tubers, rhizomes, offshoots and seeds.
Treatment accordin to the invention of the plants and plant parts with the active
compounds/active compound combinations is carried out directly or by allowin the compounds to
act on their surroundins, habitat or storae space by the customary treatment methods, for
example by immersion, sprayin, evaporation, foin, scatterin, paintin on, inection and, in the
case of propaation material, in particular in the case of seeds, also by applyin one or more coats.
The active compounds/active compound combinations can be converted to the customary
formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions,
powders, dusts, pastes, soluble powders, soluble ranules, ranules for broadcastin, suspensionemulsion
concentrates, natural materials imprenated with active compound, synthetic materials
imprenated with active compound, fertilizers and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixin the active
compounds/active compound combinations with extenders, that is liquid solvents and/or solid
carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foamformers.
If the extender used is water, it is also possible to use oranic solvents, for example, as auxiliary
solvents. Suitable liquid solvents are esentially aromatics, such as xylene, toluene or
alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as
chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as
cyclohexane or paraffins, for example petroleum fractions, mineral and veetable oils, alcohols,
such as butanol or lycol, as well as their ethers and esters, ketones, such as acetone, methyl ethyl
ketone, methyl isobutyl ketone or cyclohexanone, stronly polar solvents, such as dimethyl
sulfoxide, and also water.
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Suitable solid carriers are:
for example ammonium salts and round natural minerals such as kaolins, clays, talc, chalk,
quartz, attapulite, montmorillonite or diatomaceous earth, and round synthetic minerals such as
hihly disperse silica, alumina and silicates; suitable solid carriers for ranules are: for example
crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or
else synthetic ranules of inoranic and oranic meals, and ranules of oranic material such as
sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers
are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl polylycol ethers, alkylsulphonates,
alkyl sulfates, arylsulfonates, or else protein hydrolyzates; suitable dispersants are: for example
linosulfite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of
powders, ranules or latices, such as um arabic, polyvinyl alcohol and polyvinyl acetate, or else
natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in
the formulations. Other additives can be mineral and veetable oils.
It is possible to use colorants such as inoranic piments, for example iron oxide, titanium oxide
and Prussian blue, and oranic colorants such as alizarin colorants, azo colorants and metal
phthalocyanine colorants, and trace nutrients such as salts of iron, mananese, boron, copper,
cobalt, molybdenum and zinc.
The formulations enerally comprise between 0. and 95% by weiht of active compound,
preferably between 0.5 and 90%.
The active compound/active compound combinations accordin to the invention can be present in
their commercially available formulations, as well as in the use forms prepared from these
formulations, in a mixture with other active compounds such as insecticides, attractants, sterilizers,
bactericides, acaricides, nematicides, funicides, rowth-reulatin substances, herbicides,
safeners, fertilizers or semiochemicals.
Compounds which are suitable as mixin partners are, for example, the followin:
Funicides:
2-phenylphenol; -hydroxyquinoline sulfate; acibenzolar-S-methyl; aldimorph; amidoflumet;
ampropylfos; ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl;
benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos;
-3 -
binapacryl; biphenyl; bitertanol; blasticidin-S; bromuconazole; bupirimate; buthiobate;
butylamine; calcium polysulfide; capsimycin; captafol; captan; carbendazim; carboxin;
carpropamid; carvone; chinomethionat; chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil;
chlozolinate; clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil;
cyprofuram; Daer ; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine;
dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol; dimethomorph;
dimoxystrobin; diniconazole; dinconazole-M; dinocap; diphenylamine; dipyrithione; ditalimfos;
dithianon; dodine; drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole;
famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram; fenhexamid; fenitropan;
fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil;
flumetover; flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole;
flusulfamide; flutolanil; flutriafol; folpet; fosetyl-Al; fosetyl-sodium; fuberidazole; furalaxyl;
furametpyr; furcarbanil; furmecyclox; uazatine; hexachlorobenzene; hexaconazole; hymexazole;
imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris(albesilate); iodocarb;
ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione;
kasuamycin; kresoxim-methyl; maricozeb; maneb; meferimzone; mepanipyrim; mepronil;
metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxam; metiram; metominostrobin;
metsulfovax; mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen; nitrothal-isopropyl;
noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole;
oxycarboxin; oxyfenthiin; paclobutrazole; pefurazoate; penconazole; pencycuron; phosdiphen;
phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole; prochloraz;
procymidone; propamocarb; propanosine-sodiurri; propiconazole; propineb; proquinazid;
prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur;
pyrrolenitrine; quinconazole; quinoxyfen; quintozene; simeconazole; spiroxamine; sulfur;
tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole; thicyofen;
thifluzamide; thiophanate-methyl; thiram; tioxymid; tolclofos-methyl; tolylfluanid; triadimefon;
triadimenol; triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin;
triflumizole; triforine; triticonazole; uniconazole; validamycin A; vinclozolin; zineb; ziram;
zoxamide; (2S)-N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-
2-[(methylsulfonyl)amino]butanamide; l-(l-naphthalenyl)-lH-pyrrole-2,5-dione; 2,3,5,6-
tetrachloro-4-(methylsulfonyl)pyridine; 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; chloro-N-(2,3-dihydro-l,l,3-trimethyl-lH-inden-4-yl)-3-pyridinecarboxamide; 3,4,5-trichloro-2,6-
pyridinedicarbonitrile; actinovate; cis-l-(4-chlorophenyl)-2-(lH-l,2,4-triazol-l-yl)cycloheptanol;
methyl l-(2,3-dihydro-2,2-dimethyl-lH-inden-l-yl)-lH-imidazole-5-carboxylate; monopotassium
carbonate; N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide; N-butyl--( , -dimethylethyl)- -
oxaspiro[4.5]decane-3-amine; sodium tetrathiocarbonate; and copper salts and preparations, such
as Bordeaux mixture; copper hydroxide; copper naphthenate; copper oxychloride; copper sulfate;
cufraneb; cuprous oxide; mancopper; oxine-copper.
Bactericides:
bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasuamycin, octhilinone,
furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulfate and
other copper preparations.
Insecticides/acaricides/nematicides:
. Acetylcholine esterase (AChE) inhibitors
. Carbamates,
for example alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, bendiocarb,
benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran,
carbosulfan, cloethocarb, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate,
furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl,
pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb,
triazamate
.2 Oranophosphates,
for example acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos
(-methyl), butathiofos, cadusafos, carbophenothion, chlorethoxyfos,
chlorfenvinphos, chlormephos, chlorpyrifos (-methyl/-ethyl), coumaphos, cyanofenphos,
cyanophos, chlorfenvinphos, demeton-S-methyl, demeton-S-methyl sulfone, dialifos,
diazinon, dichlofenthion, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos,
dioxabenzofos, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos,
fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosmethilan,
fosthiazate, heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropyl
O-salicylate, isoxathion, malathion, mecarbam, methacrifos, methamidophos, methidathion,
mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion
(-methyl/-ethyl), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb,
phoxim, pirimiphos (-methyl/-ethyl), profenofos, propaphos, propetamphos, prothiofos,
prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos, sebufos, sulfotep,
sulprofos, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos,
triclorfon, vamidothion
-33-
2. Sodium channel modulators / voltae-ated sodium channel blockers
2. Pyrethroids,
for example acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin,
bioallethrin, bioallethrin-S cyclopentyl isomer, bioethanomethrin, biopermethrin,
bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin, cis-permethrin,
clocythrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, theta-,
zeta-), cyphenothrin, deltamethrin, empenthrin (IR isomer), esfenvalerate, etofenprox,
fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate, flucythrinate,
flufenprox, flumethrin, fluvalinate, fubfenprox, amma-cyhalothrin, imiprothrin,
kadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-), phenothrin (IR
trans-isomer), prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU 5525,
silafluofen, tau-fluvalinate, tefluthrin, terallethrin, tetramethrin (IR isomer), tralomethrin,
transfluthrin, ZXI 90, pyrethrins (pyrethrum)
for example acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine,
thiacloprid, thiamethoxam
3.2 Nicotine, bensultap, cartap
Acetylcholine receptor modulators
4. Spinosyns,
for example spinosad
ABA-ated chloride channel antaonists
5. Cyclodiene oranochlorines,
for example camphechlor, chlordane, endosulfan, amma-HCH, HCH, heptachlor, lindane,
methoxychlor
-34-
5.2 Fiproles,
for example acetoprole, ethiprole, fipronil, pyrafluprole, pyripole, vaniliprole
Chloride channel activators
6. Mectins,
for example avermectin, emamectin, emamectin benzoate, ivermectin, milbemycin
uvenile hormone mimetics,
for example diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene,
pyriproxifen, triprene
Ecdyson aonists/disruptors
. Diacylhydrazines,
for example chromafenozide, halofenozide, methoxyfenozide, tebufenozide
Chitin biosynthesis inhibitors
9. Benzoylureas,
for example bistrifluron, chlofluazuron, diflubenzuron, fluazuron, flucycloxuron,
flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron,
teflubenzuron, triflumuron
9.2 Buprofezin
9.3 Cyromazine
Oxidative phosphorylation inhibitors, ATP disrupters
0. Diafenthiuron
0.2 Oranotins,
for example azocyclotin, cyhexatin, fenbutatin oxide
Oxidative phosphorylation decouplers actin by interruptin the H-proton radient
. Pyrroles,
for example chlorfenapyr
-35-
.2 Dinitrophenols,
for example binapacyrl, dinobuton, dinocap, DNOC
Pae-I electron transport inhibitors
2. METIs,
for example fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad
2.2 Hydramethylnone
2.3 Dicofol
Pae-II electron transport inhibitors
Rotenone
Pae-Ill electron transport inhibitors
Acequinocyl, fluacrypyrim
Microbial disruptors of the insect ut membrane
Bacillus thuriniensis strains
Fat synthesis inhibitors
tetronic acids,
for example spirodiclofen, spiromesifen
tetramic acids,
for example spirotetramat (CAS Re. No.: 20333-25-) and 3-(2,5-dimethylphenyl)--
methoxy-2-oxo-l-azaspiro[4.5]dec-3-en-4-yl ethyl carbonate (also known as: carbonic
acid, 3-(2,5-dimethylphenyl)--methoxy-2-oxo-l-azaspiro[4.5]dec-3-en-4-yl ethyl ester,
CAS Re. No.: 3260-0-)
carboxamides,
-36-
for example flonicamid
octopamineric aonists,
for example amitraz
Inhibitors of manesium-stimulated ATPase,
proparite
benzoic acid dicarboxamides,
for example flubendiamides
nereistoxin analos
for example thiocyclam hydroen oxalate, thiosultap-sodium
Bioloicals, hormones or pheromones
azadirachtin, Bacillus spec., Beauveria spec., codlemone, Metarrhizium spec.,
Paecilomyces spec., thuriniensin, Verticillium spec.
Active compounds with unknown or unspecific mechanisms of action
23. Fumiants,
for example aluminum phosphide, methyl bromide, sulfuryl fluoride
23.2 Antifeedants,
for example cryolite, flonicamid, pymetrozine
23.3 Mite rowth inhibitors,
for example clofentezine, etoxazole, hexythiazox
23.4 Amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin,
chinomethionat, chlordimeform, chlorobenzilate, chloropicrin, clothiazoben, cycloprene,
cyflumetofen, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, flufenerim, flutenzin,
ossyplure, hydramethylnone, aponilure, metoxadiazone, petroleum, piperonyl butoxide,
potassium oleate, pyridalyl, sulfluramid, tetradifon, tetrasul, triarathene, verbutin
A mixture with other known active compounds, such as herbicides, fertilizers, rowth reulators,
safeners, semiochemicals, or else with aents which improve plant properties is also possible.
When used as insecticides in their commercially available formulations and in the use forms prepared
from these formulations, the active compounds/active compound combinations accordin to the
invention can furthermore be present in the form of a mixture with synerists. Synerists are
compounds by which the activity of the active compounds is increased without it bein necessary for
the synerist added to be active itself.
When used as insecticides in their commercially available formulations and in the use forms
prepared from these formulations, the active compounds/active compound combinations accordin
to the invention can furthermore be present in the form of mixtures with inhibitors which reduce
the deradation of the active compound after application in the habitat of the plant, on the surface
of parts of plants or in plant tissues.
The active compound content of the use forms prepared from the commercially available
formulations can vary within wide ranes. The active compound concentration of the use forms can
be from 0.0000000 up to 95% by weiht of active compound and is preferably between 0.0000 and
% by weiht.
Application is in a customary manner adapted to suit the use forms.
As already mentioned above, it is possible to treat all plants and their parts in accordance with the
invention. In a preferred embodiment, wild plant species or plant varieties and plant cultivars which
have been obtained by traditional bioloical breedin methods, such as hybridization or protoplast
fusion, and the parts of these varieties and cultivars are treated. In a further preferred embodiment,
transenic plants and plant cultivars which have been obtained by recombinant methods, if
appropriate in combination with conventional methods (enetically modified oranisms), and their
parts are treated. The term "parts" or "parts of plants" or "plant parts" has been explained above.
Plants which are treated particularly preferably in accordance with the invention are those of the plant
cultivars which are in each case commercially available or in use. Plant cultivars are understood as
meanin plants with new traits which have been bred either by conventional breedin, by
mutaenesis or by recombinant DNA techniques. They may take the form of cultivars, biotypes and
enotypes.
Dependin on the plant species or plant cultivars, their location and rowth conditions (soils, climate,
veetation period, nutrition), the treatment accordin to the invention may also result in superadditive
("syneristic") effects. Thus, for example, reduced application rates and/or a widened activity
spectrum and/or an increase in the activity of the substances and compositions which can be used in
accordance with the invention, better plant rowth, increased tolerance to hih or low temperatures,
increased tolerance to drouht or to salinity in the water or soil, increased flowerin performance,
facilitated harvestin, accelerated maturation, hiher yields, hiher quality and/or better nutritional
value of the harvested products, better storae characteristics and/or processability of the harvested
products are possible which exceed the effects which were actually to be expected.
The preferred transenic plants or plant cultivars (those obtained by recombinant methods) to be
treated in accordance with the invention include all those plants which, owin to the process of
recombinant modification, were iven enetic material which confers particular, advantaeous,
valuable traits to these plants. Examples of such properties are better plant rowth, increased
tolerance to hih or low temperatures, increased tolerance to drouht or to salinity in the water or
soil, increased flowerin performance, facilitated harvestin, accelerated maturation, hiher harvest
yields, hiher quality and/or hiher nutritional value of the harvested products, better storae
characteristics and/or better processability of the harvested products. Further examples of such traits,
examples which must be mentioned especially, are .better defense of the plants aainst animal and
microbial pests, such as aainst insects, mites, phytopathoenic funi, bacteria and/or viruses and an
increased tolerance of the plants to certain herbicidal active compounds. Examples of transenic
plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize,
soybeans, potato, suar beet, tomatoes, peas and other veetable varieties, cotton, tobacco, oilseed
rape and fruit plants (with the fruits apples, pears, citrus fruits and rapes), with particular emphasis
on maize, soybeans, potatoes, cotton, tobacco, and oilseed rape. Traits which are especially
emphasized are the increased defense of the plants aainst insects, arachnids, nematodes and slus
and snails, owin to toxins bein formed in the plants, in particular toxins which are enerated in the
plants by the enetic material of Bacillus thuriniensis (for example by the enes CrylA(a), CrylA(b),
CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and Cry IF and their combinations
(hereinbelow "Bt plants"). Other traits which are particularly emphasized are the increased defense of
plants aainst funi, bacteria and viruses by the systemic acquired resistance (SAR), systemins,
phytoalexins, elicitors and resistance enes and correspondinly expressed proteins and toxins. Other
traits which are especially emphasized are the increased tolerance of the plants to certain herbicidal
active compounds, for example imidazolinones, sulfonylureas, lyphosate or phosphinotricin (for
example "PAT" ene). The enes which confer the desired traits in each case may also be present in
the transenic plants in combination with one another. Examples of "Bt plants" which may be
mentioned are maize cultivars, cotton cultivars, soybean cultivars and potato cultivars which are
commercially available under the trade names YIELD ARD® (for example maize, cotton,
soybeans), KnockOut® (for example maize), StarLink® (for example maize), Bollard® (cotton),
Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be
mentioned are maize cultivars, cotton cultivars and soybean cultivars which are commercially
available under the trade names Roundup Ready® (tolerance to lyphosate, for example maize,
cotton, soybeans), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI®
(tolerance to imidazolinones) and STS® (tolerance to sulfonylureas, for example maize). Herbicideresistant
plants (plants bred in a conventional manner for herbicide tolerance) which may be
mentioned also include the varieties commercially available under the name Clearfield® (for example
maize). Naturally, these statements also apply to plant cultivars havin these enetic traits or enetic
traits still to be developed, which plant cultivars will be developed and/or marketed in the future.
The plants listed can be treated particularly advantaeously accordin to the invention with the
compounds of the eneral formula or the active compound mixtures accordin to the invention. The
preferred ranes stated above for the active compounds and mixtures also apply to the treatment of
these plants. Particular emphasis may be iven to the treatment of plants with the compounds or
mixtures specifically mentioned in the present text.
The active compounds/active compound combinations accordin to the invention are not only active
aainst plant, hyiene and stored-product pests, but also, in the veterinary medicine sector, aainst
animal parasites (ectoparasites and endoparasites), such as ixodid ticks, arasid ticks, scab mites,
trombiculid mites, flies (stinin and suckin), parasitic fly larvae, lice, hair lice, bird lice and fleas.
These parasites include:
From the order of the Anoplurida, for example, Haematopinus spp., Linonathus spp., Pediculus spp.,
Phtirus spp., Solenopotes spp.
From the order of the Mallophaida and the sub-orders Amblycerina and Ischnocerina, for example,
Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp.,
Damalina spp., Trichodectes spp., Felicola spp.
From the order of the Diptera and the sub-orders Nematocerina and Brachycerina, for example,
Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp.,
Lutzomyia spp., Culicoides spp., hrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp.,
Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp.,
Haematobia spp., Morellia spp., Fannia spp., lossina spp., Calliphora spp., Lucilia spp.,
Chrysomyia spp., Wohlfahrtia spp., Sarcophaa spp., Oestrus spp., Hypoderma spp., asterophilus
spp., Hippobosca spp., Lipoptena spp. and Melophaus spp.
From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopyslla
spp. and Ceratophyllus spp.
From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and
Panstronylus spp.
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela
ermanica and Supella spp.
From the sub-class of the Acari (Acarina) and the orders of the Meta- and Mesostimata, for
example, Aras spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus
spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus
spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.
From the order of the Actinedida (Prostimata) and Acaridida (Astimata), for example, Acarapis
spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorerates spp., Demodex spp.,
Trombicula spp., Listrophorus spp., Acarus spp., Tyrophaus spp., Calolyphus spp., Hypodectes
spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres
spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
The active compounds/active compound combinations of the formula (I) accordin to the invention
are also suitable for controllin arthropods which attack aricultural livestock, such as, for
example, cattle, sheep, oats, horses, pis, donkeys, camels, buffaloes, rabbits, chickens, turkeys,
ducks, eese, honeybees, other domestic animals, such as, for example, dos, cats, cae birds,
aquarium fish, and so-called experimental animals, such as, for example, hamsters, uinea-pis,
rats and mice. By combatin these arthropods, it is intended to reduce deaths and decreased
performances (in meat, milk, wool, hides, es, honey and the like), so that more economical and
simpler animal keepin is made possible by usin the active compounds accordin to the
invention.
In the veterinary sector, the active compounds/active compound combinations accordin to the
invention are used in a known manner by enteral administration, for example in the form of tablets,
capsules, drinks, drenches, ranules, pastes, boli, the feed-throuh method, suppositories, by
parenteral administration, such as, for example, by means of inections (intramuscular,
subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal application, by dermal
administration, for example in the form of dippin or bathin, sprayin, pourin-on and spottinon,
washin, dustin, and with the aid of shaped articles which comprise active compound, such as
collars, ear tas, tail marks, limb bands, halters, markin devices and the like.
When administered to livestock, poultry, domestic animals and the like, the active compounds of
the formula (I) can be used as formulations (for example powders, emulsions, flowables) which
comprise the active compounds in an amount of to 0% by weiht, either directly or after
dilution by a factor of 00 to 0 000, or they may be used in the form of a chemical bath.
Furthermore, it has been found that the compounds/active compound combinations accordin to the
invention have a potent insecticidal action aainst insects which destroy industrial materials.
The followin insects may be mentioned by way of example and as bein preferred, but without
any limitation:
Beetles, such as Hylotrupes baulus, Chlorophorus pilosis, Anobium punctatum, Xestobium
rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini,
Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,
Trooxylon aequale, Minthes ruicollis, Xyleborus spec. Tryptodendron spec. Apate monachus,
Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus;
Dermapterans, such as Sirex uvencus, Urocerus ias, Urocerus ias tainus, Urocerus auur;
Termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,
Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifuus, Mastotermes
darwiniensis, Zootermopsis nevadensis, optotermes. formosanus;
Bristletails, such as Lepisma saccharina.
Industrial materials are to be understood as meanin, in the present context, non-live materials,
such as, preferably, synthetic materials, lues, sizes, paper and board, leather, wood and timber
products, and paint.
The materials to be very particularly preferably protected aainst attack by insects are wood and
timber products.
Wood and timber products which can be protected by the composition accordin to the invention
or mixtures comprisin such a composition are to be understood as meanin, for example:
construction timber, wooden beams, railway sleepers, bride components, etties, wooden vehicles,
boxes, pallets, containers, telephone poles, wood claddin, windows and doors made of wood,
plywood, particle board, oiner's articles, or wood products which, quite enerally, are used in the
construction of houses or in oinery.
-42-
The active compounds can be used as such, in the form of concentrates or enerally customary
formulations, such as powders, ranules, solutions, suspensions, emulsions or pastes.
The formulations mentioned can be prepared in a manner known per se, for example by mixin the
active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or
fixative, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, colorants
and piments and other processin auxiliaries.
The insecticidal compositions or concentrates used for the protection of wood and wooden
materials comprise the active compound accordin to the invention in a concentration of 0.000 to
95% by weiht, in particular 0.00 to 60% by weiht.
The amount of the compositions or concentrates employed depends on the species and the
occurrence of the insects and on the medium. The optimum rate of application can be determined
upon use in each case by a test series. However, in eneral, it suffices to employ 0.000 to 20% by
weiht, preferably 0.00 to 0% by weiht, of the active compound, based on the material to be
protected.
The solvent and/or diluent used is an oranochemical solvent or solvent mixture and/or an oily or
oil-type oranochemical solvent or solvent mixture of low volatility and/or a polar oranochemical
solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wettin aent.
Oranochemical solvents which are preferably employed are oily or oil-type solvents havin an
evaporation number of above 35 and a flash point of above 30°C, preferably above 45°C.
Substances which are used as such oily and oil-type solvents which have low volatility and are
insoluble in water are suitable mineral oils or their aromatic fractions, or mineral-oil-containin
solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene.
Substances which are advantaeously used are mineral oils with a boilin rane of 70 to 220°C,
white spirit with a boilin rane of 70 to 220°C, spindle oil with a boilin rane of 250 to 350°C,
petroleum or aromatics of boilin rane 60 to 20°C, essence of turpentine and the like.
In a preferred embodiment, liquid aliphatic hydrocarbons with a boilin rane of 0 to 20°C or
hih-boilin mixtures of aromatic and aliphatic hydrocarbons with a boilin rane of 0 to 220°C
and/or spindle oil and/or monochloronaphthalene, preferably a-monochloronaphthalene, are used.
The oranic oily or oil-type solvents of low volatility havin an evaporation number of above and a flash point of above 30°C, preferably above 45°C, can be partially replaced by
oranochemical solvents of hih or medium volatility, with the proviso that the solvent mixture
also has an evaporation number of above 35 and a flash point of above 30°C, preferably above
45°C, and that the insecticide/funicide mixture is soluble or emulsifiable in this solvent mixture.
In a preferred embodiment, part of the oranochemical solvent or solvent mixture or an aliphatic
polar oranochemical solvent or solvent mixture is replaced. Substances which are preferably used
are aliphatic oranochemical solvents havin hydroxyl and/or ester and/or ether roups, such as,
for example, lycol ethers, esters and the like.
The oranochemical binders used within the scope of the present invention are the synthetic resins
and/or bindin dryin oils which are known per se and can be diluted with water and/or are soluble
or dispersible or emulsifiable in the oranochemical solvents employed, in particular binders
composed of, or comprisin, an acrylate resin, a vinyl resin, for example polyvinyl acetate,
polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or
modified alkyd resin, phenol resin, hydrocarbon resin, such as indene/cumarone resin, silicone
resin, dryin veetable and/or dryin oils and/or physically dryin binders based on a natural
and/or synthetic resin.
The synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or
solution. Up to 0% by weiht of bitumen or bituminous substances can also be used as binders. In
addition, colorants, piments, water repellents, odor-maskin substances and inhibitors or
anticorrosives known per se and the like can also be employed.
The composition or the concentrate preferably comprises, in accordance with the invention, at least
one alkyd resin or modified alkyd resin and/or a dryin veetable oil as the oranochemical binder.
Preferably used accordin to the invention are alkyd resins with an oil content of over 45% by
weiht, preferably 50 to 6% by weiht.
All or some of the abovementioned binder can be replaced by a fixative (mixture) or a plasticizer
(mixture). These additives are intended to prevent volatilization of the active compounds and
crystallization or precipitation. They preferably replace 0.0 to 30% of the binder (based on 00%
of binder employed).
The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl phthalate,
dioctyl phthalate or benzyl butyl phthalate, the phosphoric esters, such as tributyl phosphate, the
adipic esters, such as di(2-ethylhexyl) adipate, the stearates, such as butyl stearate or amyl stearate,
the oleates, such as butyl oleate, the lycerol ethers or relatively hih molecular weiht lycol
ethers, lycerol esters and p-toluenesulfonic esters.
- 44-
Fixatives are chemically based on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl
ether, or ketones, such as benzophenone or ethylenebenzophenone.
Particularly suitable as a solvent or diluent is also water, if appropriate as a mixture with one or
more of the abovementioned oranochemical solvents or diluents, emulsifiers and dispersants.
Particularly effective protection of wood is achieved by lare-scale industrial imprenation
processes, for example vacuum, double-vacuum or pressure processes.
If appropriate, the ready-to-use compositions can additionally comprise other insecticides and, if
appropriate, additionally one or more funicides.
Suitable additional components which may be admixed are, preferably, the insecticides and
funicides mentioned in WO 94/29 26. The compounds mentioned in that document are expressly
part of the present application.
Very particularly preferred components which may be admixed are insecticides, such as
chlorpyriphos, phoxim, silafluofm, alphamethrin, cyfluthrin, cypermethrin, deltamethrin,
permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid,
methoxyphenoxid, triflumuron, chlothianidin, spinosad, tefluthrin,
and funicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,
cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propynyl
butylcarbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.
The compounds accordin to the invention can at the same time be employed for protectin obects
which come into contact with saltwater or brackish water, in particular hulls, screens, nets,
buildins, moorins and sinalin systems, aainst foulin.
Foulin by sessile Oliochaeta, such as Serpulidae, and by shells and species from the
Ledamorpha roup (oose barnacles), such as various Lepas and Scalpellum species, or by species
from the Balanomorpha roup (acorn barnacles), such as Balanus or Pollicipes species, increases
the frictional dra of ships and, as a consequence, leads to a marked increase in operation costs
owin to hiher enery consumption and additionally frequent residence in the dry dock.
Apart from foulin by alae, for example Ectocarpus sp. and Ceramium sp., foulin by sessile
Entomostraka roups, which come under the eneric term Cirripedia (cirriped crustaceans), is of
particular importance.
Surprisinly, it has now been found that the compounds accordin to the invention, alone or in
combination with other active compounds, have an outstandin antifoulin action.
Usin the compounds accordin to the invention, alone or in combination with other active
compounds, allows the use of heavy metals such as, for example, in bis(trialkyltin) sulfides, tri-rcbutyltin
laurate, tri-butyltin chloride, copper(I) oxide, triethyltin chloride, tri-«-butyl-(2-phenyl-
4-chlorophenoxy)tin, tributyltin oxide.; molybdenum disulfide, antimony oxide, polymeric butyl
titanate, phenyl(bispyridine)bismuth chloride, tri-«-butyltin fluoride, mananese ethylenebisthiocarbamate,
zinc dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts and copper
salts of 2-pyridinethiol -oxide, bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate, zinc
oxide, copper(I) ethylenebisdithiocarbamate, copper thiocyanate, copper naphthenate and tributyltin
halides to be dispensed with, or the concentration of these compounds to be substantially
reduced.
If appropriate, the ready-to-use antifoulin paints can additionally comprise other active
compounds, preferably alicides, funicides, herbicides, molluscicides, or other antifoulin active
compounds.
Preferably suitable components in combination with the antifoulin compositions accordin to the
invention are:
alicides such as
2-/e-butylamino-4-cyclopropylamino-6-methylthio-l,3,5-triazine, dichlorophen, diuron, endothal,
fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
funicides such as
benzo[£]thiophenecarboxylic acid cyclohexylamide S,S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-
2-propynyl butylcarbamate, tolylfluanid and azoles such as
azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and
tebuconazole;
molluscicides such as
fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and trimethacarb, Fe chelates;
or conventional antifoulin active compounds such as
4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl sulfone, 2-(N,N-dimethylthiocarbamoylthio)-
5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol
-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4-(methylsulfonyl)-
pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6-
trichlorophenylmaleimide.
The antifoulin compositions used comprise the active compound accordin to the invention of the
compounds accordin to the invention in a concentration of 0.00 to 50% by weiht, in particular
0.0 to 20% by weiht.
Moreover, the antifoulin compositions accordin to the invention comprise the customary
components such as, for example, those described in Unerer, Chem. Ind, 95, 37, 730-732 and
Williams, Antifoulin Marine Coatins, Noyes, Park Ride, 973.
Besides the alicidal, funicidal, moliuscicidal active compounds and insecticidal active
compounds accordin to the invention, antifoulin paints comprise, in particular, binders.
Examples of reconized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a
solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl
chloride/vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of
oranic solvent systems, butadiene/styrene/acrylonitrile rubbers, dryin oils such as linseed oil,
resin esters or modified hardened resins in combination with tar or bitumens, asphalt and epoxy
compounds, small amounts of chlorine rubber, chlorinated polypropylene and vinyl resins.
If appropriate, paints also comprise inoranic piments, oranic piments or colorants which are
preferably insoluble in saltwater. Paints may furthermore comprise materials such as rosin to allow
controlled release of the active compounds. Furthermore, the paints may comprise plasticizers,
modifiers which affect the rheoloical properties and other conventional constituents. The
compounds accordin to the invention or the abovementioned mixtures may also be incorporated
into self-polishin antifoulin systems.
The active compounds are also suitable for controllin animal pests, in particular insects,
arachnids and mites, which are found in enclosed spaces such as, for example, dwellins, factory
halls, offices, vehicle cabins and the like. They can be employed in domestic insecticide products
for controllin these pests alone or in combination with other active compounds and auxiliaries.
They are active aainst sensitive and resistant species and aainst all development staes. These
pests include:
From the order of the Scorpionidea, for example, Buthus occitanus.
From the order of the Acarina, for example, Aras persicus, Aras reflexus, Bryobia ssp.,
Dermanyssus allinae, lyciphaus domesticus, Ornithodorus moubat, Rhipicephalus sanuineus,
Trombicula alfredduesi, Neutrombicula autumnalis, Dermatophaoides pteronissimus,
Dermatophaoides forinae.
From the order of the Araneae, for example, Aviculariidae, Araneidae.
From the order of the Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones
cheiridium, Opiliones phalanium.
From the order of the Isopoda, for example, Oniscus asellus, Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus uttulatus, Polydesmus spp.
From the order of the Chilopoda, for example, eophilus spp.
From the order of the Zyentoma, for example, Ctenolepisma spp., Lepisma saccharina,
Lepismodes inquilinus.
From the order of the Blattaria, for example, Blatta orientalies, Blattella ermanica, Blattella
asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae,
Periplaneta americana, Periplaneta brimnea, Periplaneta fuliinosa, Supella lonipalpa.
From the order of the Saltatoria, for example, Acheta domesticus.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Kalotermes spp., Reticulitermes spp.
From the order of the Psocoptera, for example, Lepinatus spp., Liposcelis spp.
From the order of the Coleptera, for example, Anthrenus spp., Attaenus spp., Dermestes spp.,
Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus ranarius,
Sitophilus oryzae, Sitophilus zeamais, Steobium paniceum.
From the order of the Diptera, for example, Aedes aeypti, Aedes albopictus, Aedes
taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex
quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca
domestica, Phlebotomus spp., Sarcophaa carnaria, Simulium spp., Stomoxys calcitrans, Tipula
paludosa.
From the order of the Lepidoptera, for example, Achroia risella, alleria mellonella, Plodia
interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis,
Pulex irritans, Tuna penetrans, Xenopsylla cheopis.
From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliinosus,
Lasius nier, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
From the order of the Anoplura, for example, Pediculus humanus capitis, Pediculus humanus
corporis, Phthirus pubis.
From the order of the Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus
prolixus, Triatoma infestans.
They are used in the household insecticides sector alone or in combination with other suitable
active compounds such as phosphoric esters, carbamates, pyrethroids, neonicotinoids, rowth
reulators or active compounds from other known classes of insecticides.
They are used in aerosols, pressure-free spray products, for example pump and atomizer sprays,
automatic foin systems, foers, foams, els, evaporator products with evaporator tablets made
of cellulose or polymer, liquid evaporators, el and membrane evaporators, propeller-driven
evaporators, enery-free, or passive, evaporation systems, moth papers, moth bas and moth els,
as ranules or dusts, in baits for spreadin or in bait stations.
The active compounds/active compound combinations accordin to the invention can also be used
as defoliants, desiccants, haulm killers and, in particular, as weed killers. Weeds in the broadest
sense are understood as meanin all plants which row at locations where they are undesired.
Whether the substances accordin to the invention act as nonselective or selective herbicides
depends essentially on the application rate.
The active compounds/active compound combinations accordin to the invention can be used, for
example, in the followin plants:
Dicotyledonous weeds of the enera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis,
Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium,
Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, aleopsis, alinsoa, alium,
Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis,
Mulluo, Myosotis, Papaver, Pharbitis, Plantao, Polyonum, Portulaca, Ranunculus, Raphanus,
Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus,
Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
icotyledonous crops of the enera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus,
Daucus, lycine, ossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus,
Pisum, Solanum, Vicia.
Monocotyledonous weeds of the enera: Aeilops, Aropyron, Arostis, Alopecurus, Apera,
Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Diitaria,
Echinochloa, Eleocharis, Eleusine, Erarostis, Eriochloa, Festuca, Fimbristylis, Heteranthera,
Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum,
Poa, Rottboellia, Saittaria, Scirpus, Setaria, Sorhum.
Monocotyledonous crops of the enera: Allium, Ananas, Asparaus, Avena, Hordeum, Oryza,
Panicum, Saccharum, Secale, Sorhum, Triticale, Triticum, Zea.
However, the use of the active compounds/active compound combinations accordin to the
invention is in no way restricted to these enera, but extends in the same manner to other plants.
Dependin on the concentration, the active compounds/active compound combinations accordin
to the invention are suitable for the nonselective weed control on, for example, industrial terrains
and railway tracks and on paths and locations with and without trees. Likewise the active
compounds accordin to the invention can be employed for controllin weeds in perennial crops,
for example forests, ornamental tree plantins, orchards, vineyards, citrus roves, nut orchards,
banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations,
cocoa plantations, soft fruit plantations and hop fields, on lawns, turf and pastureland, and for the
selective control of weeds in annual crops.
The compounds of the formula (I)/active compound combinations accordin to the invention have
stron herbicidal activity and a broad activity spectrum when used on the soil and on aerial plant
parts. To a certain extent, they are also suitable for the selective control of monocotyledonous and
dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre- and postemerence.
At certain concentrations or application rates, the active compounds/active compound
combinations accordin to the invention can also be employed for controllin animal pests and
funal or bacterial plant diseases. If appropriate, they can also be used as intermediates or
precursors for the synthesis of other active compounds.
The active compounds/active compound combinations can be converted into the customary
formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dustin aents,
pastes, soluble powders, ranules, suspoemulsion concentrates, natural and synthetic materials
imprenated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixin the active compounds
with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that
is emulsifiers and/or dispersants and/or foam-formers.
If the extender used is water, it is also possible to use, for example, oranic solvents as auxiliary
solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes,
chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes,
chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for
example petroleum fractions, mineral and veetable oils, alcohols, such as butanol or lycol, and also
their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or
cyclohexanone, stronly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and also
water.
Suitable solid carriers are: for example ammonium salts and round natural minerals, such as kaolins,
clays, talc, chalk, quartz, attapulite, montmorillonite or diatomaceous earth, and round synthetic
minerals, such as finely divided silica, alumina and silicates, suitable solid carriers for ranules are:
for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and
dolomite, and also synthetic ranules of inoranic and oranic meals, and ranules of oranic
material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or
foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid
esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polylycol ethers, alkylsulfonates,
alkyl sulfates, arylsulfonates and protein hydrolyzates; suitable dispersants are: for example linosulfite
waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of
powders, ranules or latices, such as um arabic, polyvinyl alcohol and polyvinyl acetate, and also
natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the
formulations. Other possible additives are mineral and veetable oils.
It is possible to use colorants such as inoranic piments, for example iron oxide, titanium oxide and
Prussian blue, and oranic colorants, such as alizarin colorants, azo colorants and metal phthalocyanine
colorants, and trace nutrients such as salts of iron, mananese, boron, copper, cobalt,
molybdenum and zinc.
The formulations enerally comprise between 0. and 95 per cent by weiht of active compound,
preferably between 0.5 and 90%.
The active compounds/active compound combinations accordin to the invention, as such or in
their formulations, can also be used for weed control purposes as a mixture with known herbicides
and/or with substances which improve crop plant tolerance ("safeners"), ready mixes or tank mixes
bein possible. Mixtures with herbicide products which contain one or more known herbicides and
a safener are hence also possible.
Herbicides which are suitable for the mixtures are known herbicides, for example
acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne,
amicarbazone, amidochlor, amidosulfuron, aminopyralid, anilofos, asulam, atrazine, azafenidin,
azimsulfuron, beflubutamid, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone,
bencarbazone, benzfendizone, benzobicyclon, benzofenap, benzoylprop (-ethyl), bialaphos,
bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil
(-allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone (-ethyl),
chlomethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron,
chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop
(-proparyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam (-methyl),
cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-
D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (-P), diclofop (-methyl), diclosulam,
diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor,
dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron,
dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron (-methyl), ethofumesate,
ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop (-P-ethyl), fentrazamide, flamprop
(-isopropyl, -isopropyl-L, -methyl), flazasulfuron, florasulam, fluazifop (-P-butyl), fluazolate,
flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn,
flumetsulam, fluometuron, fluorochloridone, fluorolycofen (-ethyl), flupoxam, flupropacil,
flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (-butoxypropyl,
-meptyl), flurprimidol, flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron,
lufosinate (-ammonium), lyphosate (-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl,
-P-methyl), hexazinone, HOK-20, imazamethabenz (-methyl), imazamethapyr, imazamox,
imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium),
ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop,
KIH 45, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesosulfuron, mesotrione,
metamifop, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)
metolachlor, metosulam, metoxuron, metribuzin, metsulfuron (-methyl), molinate, monolinuron,
naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron,
oryzalin, oxadiaryl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelaronic
acid, pendimethalin, pendralin, penoxsulam, pentoxazone, phenmedipham, picolinafen, pinoxaden,
piperophos, pretilachlor, primisulfuron (-methyl), profluazol, prometryn, propachlor, propanil,
propaquizafop, propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb,
prosulfuron, pyraflufen (-ethyl), pyrasulfotole, pyrazoyl, pyrazolate, pyrazosulfuron (-ethyl),
pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol, pyriftalide, pyriminobac (-methyl),
pyrimisulfan, pyrithiobac (-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop (-P-ethyl,
-P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron
(-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tembotrione, tepraloxydim,
terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron
(-methyl), thiobencarb, tiocarbazil, topramezone, tralkoxydim, triallate, triasulfuron, tribenuron
(-methyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron
and
A mixture with other known active compounds, such as funicides, insectides, acaricides,
nematicides, bird repellents, plant nutrients and soil conditioners, is also possible.
The active compounds/active compound combinations can be applied as such, in the form of their
formulations or the use forms prepared therefrom by further dilution, such as ready-to-use
solutions, suspensions, emulsions, powders, pastes and ranules. They are applied in the
customary manner, for example by pourin, sprayin, atomizin, spreadin.
The active compounds/active compound combinations accordin to the invention can be applied
both before and after plant emerence. They can also be incorporated into the soil prior to.
plantin.
The application rate of active compound can vary within a substantial rane. Essentially, it
depends on the nature of the desired effect. In eneral, the application rates are between and
0 k of active compound per hectare of soil area, preferably between 5 and 5 k per ha.
The advantaeous effect of the compatibility with crop plants of the active compound
combinations accordin to the invention is particularly pronounced at certain concentration ratios.
However, the weiht ratios of the active compounds in the active compound combinations can be
varied within relatively wide ranes. In eneral, from 0.00 to 000 parts by weiht, preferably
from 0.0 to 00 parts by weiht, particularly preferably 0.05 to 20 parts by weiht, of one of the
compounds which improves crop plant compatibility (antidotes/safeners) mentioned above under
(b) are present per part by weiht of active compound of the formula (I).
The active compound combinations accordin to the invention are enerally applied in the form of
finished formulations. However, the active compounds contained in the active compound
combinations can, as individual formulations, also be mixed durin use, i.e. be applied in the form
of tank mixes.
For certain applications, in particular by the post-emerence method, it may furthermore be
advantaeous to include, as further additives in the formulations, mineral or veetable oils which
are compatible with plants (for example the commercial preparation "Rako Binol"), or ammonium
salts, such as, for example, ammonium sulfate or ammonium thiocyanate.
The novel active compound combinations can be used as such, in the form of their formulations or
the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions,
emulsions, powders, pastes and ranules. Application is in the customary manner, for example by
waterin, sprayin, atomizin, dustin or scatterin.
The application rates of the active compound combinations accordin to the invention can be
varied within a certain rane; they depend, inter alia, on the weather and on soil factors. In eneral,
the application rates are between 0.00 and 5 k per ha, preferably between 0.005 and 2 k per ha,
particularly preferably between 0.0 and 0.5 k per ha.
The active compound combinations accordin to the invention can be applied before and after
emerence of the plants, that is to say by the pre-emerence and post-emerence method.
Dependin on their properties, the safeners to be used accordin to the invention can be used for
pretreatin the seed of the crop plant (seed dressin) or can be introduced into the seed furrows
prior to sowin or be used separately prior to the herbicide or toether with the herbicide, before or
after emerence of the plants.
Preparation and use of the active compounds accordin to the invention are illustrated in the
examples below.
Under aron, 5.24 of potassium tert-butoxide-95% pure- (44.4 mmol) are initially chared in
0ml of dimethylacetamide in a 00 ml three-necked flask fitted with thermometer and reflux
condenser.
At 40 to 50°C, .7 of the compound accordin to Example II-l (20.2 mmol) in 0ml of
dimethylacetamide are added dropwise. The mixture is stirred at 60°C for h and monitored by
thin-layer chromatoraphy durin this time.
The reaction solution is then stirred into 00 ml of ice-water, the pH is adusted to 2 usin cone.
HC and the precipitate is filtered off with suction. The product is then purified by column
chromatoraphy on silica el (dichloromethane:ethyl acetate 5:3).
Yield 7. (94% of theory), m.p. 225.6°C.
(3 mmol) of example I-l-c-4 from WO 97/02243 are initially chared in
30 ml of anhydrous tetrahydrofuran in a 00 ml three-necked flask. At -7°C, 2.64 ml of nbutyllithium
(2.5m in n-hexane) are added dropwise. After 5 min of stirrin, 0.76 (3 mmol) of
iodine in 5 ml of anhydrous tetrahydrofuran is added dropwise at -7°C, and the mixture is allowed
to slowly warm to room temperature. The solvent is evaporated and the residue is pre-purified by
flash chromatoraphy on silica el usin the mobile phase methylene chloride/acetone 5:. The
product-containin fractions were combined, the solvent was removed under reduced pressure and
the residue 250 m was purified by reversed-phase chromatoraphy usin acetonitrile/water
(radient proram 70:30 -» 0:90). Yield: 40 m (4 2.7% of theory) m.p. 245°C.
The followin compounds of the formula (I-l-a) are obtained analoously to example (I-l-a-) and in accordance with the eneral statements on the
(Figure Removed)

Under an atmosphere of protective as, 0.4 of the compound of example I-l-a-5 is initially
chared in 30 ml of ethyl acetate, 0.5 ml of triethylamine and 0 m of Stelich base are added
and 0.5 of cyclopropylcarbonyl chloride in 5 ml of ethyl acetate is added dropwise under
reflux and the mixture is stirred further under reflux.
After the reaction has ended (monitored by thin-layer chromatoraphy) the product is purified by
flash column separation on silica el (mobile phase ethyl acetate)
Yield: 0.4 (75% of theory), m.p. 67°C
The followin compounds of the formula (I-l-b) are obtained analoously to example (I-l-b-) and in accordance with the eneral statements on the
Under aron, 0.66 (.5 mmol) of example I-l-a-2 is initially chared in 20ml of anhydrous
methylene chloride in a 00 ml three-necked flask, 0.2 ml (.5 mmol) of triethylamine is added
and 0.4 ml (.5 mmol) of ethyl chloroformate is added dropwise at 20°C. The mixture is stirred
for 4 hours, the solvent is evaporated under reduced pressure and the residue is chromatoraphed
on silica el usin the mobile phase methylene chloride/ethyl acetate 0:.
Yield: 0.4 (A 43% of theory) m.p. 9°C
The followin compounds of the formula (I-l-c) are obtained analoously to example (I-l-c-) and in accordance with the eneral statements on the if-.
preparation
Under aron, 5. of methyl cis-l-amino-4-methoxycycIohexanecarboxylate hydrochloride
(0.0226 mol) are initially chared under aron in 50 ml of anhydrous tetrahydrofuran in a 00 ml
three-necked flask fitted with thermometer and reflux condenser. At 20°C, 6.3 ml (0.0452 mol) of
triethylamine are added dropwise. The mixture is stirred for 5 min, and 5.4 of 2-iodophenylacetic
acid (0.0205 mol) are added at 20°C. After 5 min, 4.3 ml of triethylamine (0.030 mol) are added
dropwise, immediately followed by .5 ml of phosphorus oxychloride; the solution should boil
ently. The mixture is stirred under reflux for another 30 min. After coolin and removal of the
solvent under reduced pressure, the pro'duct is purified by column chromatoraphy on silica el
(dichloromethane:ethyl acetate 3:)
Yield: .7 (96% of theory), m.p. 52°C
. (4.5 mmol) of the compound of example XXIX- in 20 nil of methylene chloride are added
dropwise to .4 ml of concentrated sulfuric acid, and the mixture is stirred at an external
temperature of 30 - 40°C for 2 hours. 3.3 ml of methanol are then added dropwise, the mixture is
stirred at an external temperature of 40 - 70°C for 4 hours, allowed to stand overniht and stirred
at 40 to 70°C for a further 3 hours. The reaction solution is then poured onto ice/H2O and
extracted with dichloromethane, and the extracts are washed with sat. NaHCC3 solution, dried and
concentrated usin a rotary evaporator.
(CDC3 300 MHz): S = 7.40 (s, 2H, Ar-H), 3.65 (s, 3H, OCH3), 3.55 (s, 2H, CH2) .90
(sept, lH,CH(CH3)2)ppm.
The followin compounds of the formula (II) are obtained analoously to examples (II-l) and (II-
25) and in accordance with the eneral statements on the preparation
.7 (5.59mmol) of 4-iodo-2-ethyl-6-methylphenylacetic acid are initially chared in 25ml of
tetrahydrofuran, 2 ml of triethylamine and 0.627 (5.59 mmol) of 2-amino-2-
methylisobutyronitrile are added, the mixture is stirred at room temperature for 5 minutes, ml of
triethylamine is added followed by the dropwise addition of 0.6 ml of phosphorus oxychloride
such that the mixture boils ently. The mixture is stirred under reflux for 30 minutes, concentrated
on a rotary evaporator and worked up with ethyl acetate/water, and the oranic phase is dried with
sodium sulfate, stirred with silica el, filtered off and concentrated usin a rotary evaporator.
Yield: .2 (74% of theory), m.p. 6°C
of the formula (XXIX) are obtained analoously to example (XXIX-)
and in accordance with the eneral statements on the preparation
2-iodophenylacetyl chloride and 0.66 (5 mmol) of ethyl 2-methyl-2-hydroxypropionate
are heated at 40°C for 0 h, after coolin, 0 ml of dimethylformamide are added, and
6 ml of M potassium t-butoxide solution (6 mmol) are added dropwise. The mixture is stirred at
room temperature for 0 h and concentrated usin a rotary evaporator, and the residue is
partitioned between water and ethyl acetate. The aqueous phase is acidifed with 2N HC and the
product is extracted with ethyl acetate, the oranic phase is dried and concentrated usin a rotary
evaporator.
Yield: . (6% of theory)
loP .0
The followin compounds of the formula (I-2-a) are obtained analoously to example (I-2-a-l) in accordance with the eneral statements on the preparation
0.25 (0.757mmol) of the compound of example I-2-a-l and 0.092 (0.909 mmol) of
triethylamine are initially chared in 0ml of dichloromethane, 0.097 (0.909 mmol) of
isobutyryl chloride is added dropwise and the mixture is stirred at room temperature overniht,
washed with 0% strenth citric acid and 0% strenth aqueous sodium hydroxide solution, dried
and concentrated usin a rotary evaporator. The crude product is purified by column
chromatoraphy on silica el (radient dichloromethane dichloromethane/ethyl acetate 95:5).
Yield: 0.23 (74% of theory), loP 3.53
The followin compounds of the formula (I-2-b) are obtained analoously to example (I-2-b-l) and in accordance with the eneral statements on the
preparation
0.25 (0.757 mmol) of the compound of example I-2-a-l and 0.092 (0.909 mmol) of
triethylamine are initially chared in 0 ml of dichloromethane, 0. (0.909 mmol) of isopropyl
chloroformate is added dropwise, and the mixture is stirred at room temperature overniht, washed
with 0% strenth citric acid and 0% strenth aqueous sodium hydroxide solution, dried and
concentrated usin a rotary evaporator. The crude product is purified by column chromatoraphy
on silica el (radient dichloromethane dichloromethane/ethyl acetate 95:5).
Yield: 0.6 (46% of theory), loP 3.47
The followin compounds of the formula (I-2-c) are obtained analoously to example (I-2-c-) and in accordance with the eneral statements on the
preparation
0.566 of potassium tert-butoxide is initially chared in 5 ml of N,N-dimethylacetamide at 50°C,
of the compound of example (XII-) in 5 ml of N,N-dimethylacetamide is added and the
mixture is stirred at 60°C for 2 h. The cooled reaction solution is then added dropwise to icewater/
concentrated HC. The crystals are filtered off with suction.
Yield: 0.54 (6% of theory), m.p. 229°C
Example I--b-l
0.25 (0.00 mol) of the compound of example I--a-l and 0.074 of 2-methylpropionyl chloride
are initially chared in 5 ml of toluene at room temperature, 0. ml of triethylamine is added
5 dropwise, the mixture is stirred for 2 h, water is added and the mixture is extracted. The oranic
phase is dried and concentrated usin a rotary evaporator, and the residue is crystallized usin
n-heptane and a little ethyl acetate.
Yield: 0. (32% of theory)
]H-NMR (300 MHz, CDC3): 5 = 7.40 ppm (s, 2H, Ar-H), 3.0 ppm (m, 2H, N-CH2), 3.40 ppm
0 (m, 2H,N-CH2), 2.40 ppm (sept, H, CHC(CH3)2), 2.00-.0 ppm (m, 4H, 2 xCH2 cycle).
Example No. (I--b-2) is obtained analoously to example (I--b-l)
(300 MHz, CDC3): S = 7.40 (s, 2H, Ar-H), 3.90 (m, 2H, N-CH_2), 3.40 (m, 2H, N-CH2),
2.60-2.40 (m, 2H, Ar-CH2) ppm.
Example I--c-l
0.07 ml of ethyl chloroformate is added to 0.25 (0.00 mol) of the compound of example I--a-l
and 0. ml of triethylamine and 5 ml of toluene, and the mixture is stirred at room temperature
for hour. The reaction solution is extracted with water and the oranic phase is dried.
Purification is carried out by HPLC.
Yield: 0.09 (29% of theory)
(300 MHz, CDCI3): 5 = 7.40 (s, 2H, Ar-H), 4.5 (q, 2H, O-CH2), 3.0 (tr, 2H, N-CH2),
3.45 (tr, 2H, Ar-CH2), 2.50 (m, 2H, Ar-CH2), 2.00- .0 (m, 4H, 2 x CH2
.3 ml of triethylamine are added to 2 of 4-iodo-2-ethyl-6-methylphenylacetic acid in 40 ml of
tetrahydrofuran, and the mixture is stirred for 5 minutes. .095 of ethyl hexahydropyridazine
carbamate are then added, the mixture is stirred for 0 minutes and .92 ml of triethylamine are
added. Immediately afterward, 0.55 ml of phosphoryl chloride is slowly added dropwise. The
mixture is stirred under reflux for 30 minutes.
After coolin, the mixture is concentrated usin a rotary evaporator, the residue is worked up with
ethyl acetate/water and the oranic phase is separated off, dried with sodium sulfate, filtered off
and concentrated usin a rotary evaporator.
Yield: 2.5 (5% of theory)
]H-NMR (400 MHz, CDC3): = .5, .30 (2 t, 6H, OCH2CH3, Ar CH2CH3), 2.20 (s, 3H,
Ar-CH3), 2.50 (q, 2H, Ar-CH2CH3), 3.60, 3.70 (2d, 2H, NCH2), 7.40 (s, 2H, Ar-H) ppm.
Under aron, a solution of 0 of methyl (4-bromo-2-methyl-6-ethylphenyl)acetate, .056 of
sodium iodide, 7.023 of copper(I) iodide and 3.72 of N,N'-dimethylethylenediamine in
250 ml of dioxane is heated at 0°C for h. After the reaction has ended, the reaction mixture filtered and the mother liquor is diluted with 300 ml of water and extracted twice with 200 ml of
dichloromethane. The oranic phase is washed with 25% strenth ammonia solution, dried over
sodium sulfate and freed from the solvent. Yield of methyl (2-ethyl-4-iodo-6-
methylphenyl)acetate: 7. , 65%. 'H-NMR (300MHz, d6-DMSO): 6 = 7.42 (d, H), 7.39 (d,
H), 3.6 (s, 2 H), 3.6 (s, 3 H), 2.55 (q, 2 H), 29 (s, 3 H), .0 (t, 3 H) ppm.
(Figure Removed)
Example XXVII-
A solution of 0.696 of LiOH in 50 ml of water is added to a solution of 7.7 of methyl (2-ethyl-
4-iodo-6-methylphenyl)acetate in 50 ml of THF, and the mixture is stirred at room temperature h. The mixture is then evaporated to dryness usin a rotary evaporator, and in each case 50 ml
of ethyl acetate and water are added to the residue. The phases are separated and the ethyl acetate
phase is washed with water. The combined aqueous phases are adusted to pH = usin HC, and
the precipitated solid is filtered off with suction, washed with water and dried under reduced
pressure. Yield of (2-ethyl-4-iodo-6-methylphenyl)acetic acid: 6 , 7%.
!H-NMR (300MHz, d6-DMSO): = 2.5 (s(br), H), 7.40 (d, H), 7.3 (d, H), 3.57 (s, 2 H),
2.56 (q, 2 H), .09 (t, 3 H) ppm.
Example XXXI-2
Under aron, a solution of 20 of methyl (5-bromo-2-methylphenyl)acetate, 24.663 of sodium
iodide, 5.66 of copper(I) iodide and 7.075 of N,N'-dimethylethylenediamine in 500ml of
dioxane is heated at 0°C for 3 days. Another of sodium, 5.5 of copper(I) iodide and 3.3
of N,N'-dimethylethylenediamine are then added. After a further 3 days of heatin at 0°C, the
reaction mixture is filtered and the mother liquor is diluted with 300 ml of water and extracted
twice with 200 ml of dichloromethane. The oranic phase is washed with 25% strenth ammonia
solution, dried over Na2SO4 and freed from the solvent. Yield of methyl (5-iodo-2-
methylphenyl)acetate: .6 , 30%.
]H-NMR (300MHz, d6-DMSO): 5 = 7.56 (d, H), 7.5 (d, H), 6.99 (d, H), 3.62 (s, 2 H), 3.57
(s, 3H),2.6(s,3H)ppm.
Example XXVII-2
A solution of .04 of LiOH in 75 ml of water is added to a solution of 0.7 of methyl (5-iodo-
2-methylphenyl)acetate in 75 ml of THF, and the mixture is stirred at room temperature for h.
The mixture is then concentrated to dryness usin a rotary evaporator, and in each case 75 ml of
ethyl acetate and water are added to the residue. The phases are separated and the oranic phase is
washed with water. The combined aqueous phases are adusted to pH = usin HC and the
precipitated solid is triturated successively with dichloromethane and ethyl acetate, filtered off
(Figure Removed)
with suction and dried under reduced pressure. For further purification, it is triturated with diethyl
ether and filtered off. Yield of (5-iodo-2-methylphenyl)acetic acid: 5.5 , 44%.
(300MHz, d6-DMSO): S = 2.2 (s, (br) H), 7.55 (d, H), 7.49 (d, H), 6.9 (d, H),
3.56 (s, 2H),2.7 (s, 3 H) ppm.
The followin compounds of the formula (XXXI) are obtained analoously to examples (XXXI- -
The loP values iven in the Tables and Preparation Examples above are determined in
accordance with EEC Directive 79/3 Annex V.A by HPLC (Hih Performance Liquid
Chromatoraphy) on a reversed-phase column (C ). Temperature: 43°C.
The determination is carried out in the acidic rane at pH 2.3 usin the mobile phases 0.%
aqueous phosphoric acid and acetonitrile; linear radient from 0% acetonitrile to 95%
acetonitrile.
The LC-MS determination in the acidic rane is carried out at pH 2.7 usin the mobile phases
0.% aqueous formic acid and acetonitrile (contains 0.% formic acid); linear radient from 0%
acetonitrile to 95% acetonitrile.
The LC-MS determination in the neutral rane is carried out at pH 7. usin the mobile phases
0.00 molar aqueous ammonium bicarbonate solution and acetonitrile; linear radient from 0%
acetonitrile to 95% acetonitrile.
Calibration is carried out usin unbranched alkan-2-ones (havin 3 to 6 carbon atoms) with
known loP values (determination of the loP values by the retention times usin linear
interpolation between two successive alkanones).
The lambda max values were determined in the maxima of the chromatoraphic sinals usin the
UV spectra from 200 nm to 400 nm.
Phaedon Test (Spray treatment)
Solvents: 7 parts by weiht of acetone
.5 parts by weiht of dimethylformamide
Emulsifier: 0.5 part by weiht of alkylaryl polylycol ether
To produce a suitable preparation of active compound, part by weiht of active compound is
mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with
emulsifier-containin water to the desired concentration.
Discs of Chinese cabbae (Brassica pekinensis) are sprayed with an active compound preparation
of the desired concentration and, after dryin, populated with larvae of the mustard beetle
(Phaedon cochleariae).
After the desired period of time, the effect in % is determined. 00% means that all beetle larvae
have been killed; 0% means that none of the beetle larvae have been killed.
In this test, for example, the followin compounds of the Preparation Examples show, at an
application rate of 500 /ha, an efficacy of 0%.
Myzus Test (Spray treatment)
Solvents: 7 parts by weiht of acetone
.5 parts by weiht of dimethylformamide
Emulsifier: 0.5 part by weiht of alkylaryl polylycol ether
To produce a suitable preparation of active compound, part by weiht of active compound is
mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with
emulsifier-containin water to the desired concentration.
Discs of Chinese cabbae (Brassica pekinensis) which are infested by all staes of the reen peach
aphid {Myzus persicae) are sprayed with an active compound preparation of the desired
concentration.
After the desired period of time, the effect in % is determined. 00% means that all aphids have
been killed; 0% means that none of the aphids have been killed.
In this test, for example, the followin compounds of the Preparation Examples show, at an
application rate of 500 /ha, an efficacy of 0%.
Nilaparvata luens Test (hydroponic treatment)
Solvents: 7 parts by weiht of acetone
.5 parts by weiht of dimethylformamide
Emulsifier: 0.5 part by weiht of alkylaryl polylycol ether
To produce a suitable preparation of active compound, part by weiht of active compound is
mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with
emulsifier-containin water to the desired concentration.
The active compound preparation is pipetted into water. The stated concentration refers to the
amount of active compound per volume unit of water (m/ = ppm). After the desired period time, the water is infected with the brown plant hopper (Nilaparvata luens).
After the desired period of time, the effect in % is determined. 00% means that all plant hoppers
have been killed; 0% means that none of the plant hoppers have been killed.
In this test, the compound of Preparation Example I-2-a-2 showed, at a concentration of 20
Tetranychus Test; OP-resistant/spray treatment (TETRUR)
Solvents: 7 parts by weiht of acetone
.5 parts by weiht of dimethyIformamide
Emulsifier: 0.5 part by weiht of alkylaryl polylycol ether
To produce a suitable preparation of active compound, part by weiht of active compound is
mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with
emulsifier-containin water to the desired concentration.
Discs of bean leaves (Phaseolus vularis) which are heavily infested by all staes of the
reenhouse red spider mite (Tetranychus urticae} are sprayed with an active compound preparation
of the desired concentration.
After the desired period of time, the effect in % is determined. 00% means that all spider mites
have been killed; 0% means that none of the spider mites have been killed.
In this test, for example, the followin compounds of the Preparation Examples show, at an
application rate of 00 /ha, an efficacy of 0%.
M-a-2, I-l-a-4, I-l-a-5, I-l-a-7, I-l-a-, I-l-a-2, I-l-a-,-l-a-9, I-l-a-2,-l-a-2,-l-a-22,-
l-b-2,I-l-b-,-l-c-,-l-c-4,-l-c-5,-l-c-20,-2-a-6,-2-b-2,-2-b-5,-2-b-6, -2 b-,-2-b-0,
I-2-b-ll, I-2-C-2,-2-C-3, I-2-C-4,-2-c-S, I--b-l, I--b-2.
In this test, for example, the followin compound of the Preparation Example showed, at an
application rate of 500 /ha, an efficacy of 0%:
Herbicidal pre-emerence action
Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in
wood fiber pots and covered with soil. The test compounds, formulated in the form of wettable
powders (WP) or as emulsion concentrates (EC), are then, as an aqueous suspension with a water
application rate of 00 /ha (converted), with 0.2% of wettin aent added, applied to the surface
of the coverin soil.
After the treatment, the pots are placed in a reenhouse and kept under rowth conditions for the
test plants. The visual assessment of the emerence damae on the test plants is carried out after a
trial period of 3 weeks by comparison with untreated controls (herbicidal effect in percent (%):
(Figure Removed)
00% effect = the plants have died, 0% effect = like control plants).
Here, the followin compounds, for example, controlled Avena sativa, Lolium multiflorum and
Setaria viridis at an application rate of 320 /ha with 70% efficacy:
I-l-a-,-l-a-4,-l-a-2,-l-b-7.
- 94-
Example F
Herbicidal post-emerence action
Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in
wood fiber pots, covered with soil and cultivated in a reenhouse under ood rowth conditions.
Two to three weeks after sowin, the test plants are treated at the one-leaf stae. The test
compounds, formulated as wettable powders (WP) or as emulsion concentrates (EC), are then, as
an aqueous suspension with a water application rate of 00 /ha (converted), with 0.2% of wettin
aent added, sprayed onto the reen parts of the plants. After the test plants have been kept in the
reenhouse under optimum rowth conditions for about 3 weeks, the effect of the preparations is
rated visually in comparison to treated controls (herbicidal effect in percent (%): 00% effect = the
plants have died, 0% effect = like control plants).
Here, the followin compounds, for example, controlled Avena sativa, Echinochloa crus-alli,
Lolium multiflorum and Setaria viridis at an application rate of 320 /ha with 70% efficacy:
I-l-a-, I-l-a-n, I-l-a-2, I-l-a-3, I-l-a-4, I-l-a-2, I-l-c-, I-l-c-6, I-l-c-, I-l-c-2,-2-b-0,
I-2-C-3,--b-2.
Example
Herbicidal post-emerence action
Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed into sandy loam
in wood fiber pots or in plastic pots, covered with soil and cultivated in a reenhouse, durin the
veetation period also outdoors outside of the reenhouse, under ood rowth conditions. Two to
three weeks after sowin, the test plants are treated at the one- to three-leaf stae. The test
compounds, formulated as wettable powders (WP) or liquid (EC), are, in various dosaes at a
water application rate of 300 /ha (converted), with wettin aent (0.2 to 0.3%) added, sprayed
onto the plants and the surface of the soil. Three to four weeks after the treatment of the test plants,
the effect of the preparations is rated visually in comparison to treated controls (herbicidal effect in
%) (%): 00% effect = the plants have died, 0% effect = like control plants).
Use of safeners
If it is additionally to be tested as to whether safeners can improve the plant compatibility of test
substances in the case of crop plants, the followin options are used for applyin the safener:
seeds of the crop plants are, before sowin, dressed with the safener substance (the amount of
safener stated in percent, based on the weiht of the seed)
before the application of the test substances, the crop plants are sprayed with the safener at a
certain application rate per hectare (usually day before the application of the test
substances)
the safener is applied toether with the test substance as a tank mix (the amount of safener is
stated in /ha or as a ratio, based on the herbicide).
By comparin the effect of test substances on crop plants without or with safener treatment, it is
possible to assess the effect of the safener substance.
Container trials with cereal in a reenhouse
Mefenpyr day prior to herbicide application
(Figure Removed)
Critical concentration test/Soil insects - Treatment of transenic plants
Test insect: Diabrotica balteata - larvae in the soil
Solvent: 7 parts by weiht of acetone
Emulsifier: part by weiht of alkylaryl polylycol ether
To produce a suitable preparation of active compound, part by weiht of active compound is
mixed with the stated amount of solvent, the stated amount of emulsifier is added and the
concentrate is diluted with water to the desired concentration.
The preparation of active compound is poured onto the soil. Here, the concentration of active
compound in the preparation is virtually immaterial; only the amount by weiht of active
compound per unit volume of soil, which is stated in ppm (m/), matters. The soil is filled into
0.25 pots, and these are allowed to stand at 20°C.
Immediately after the preparation, 5 preerminated corn rains of the cultivar YIELD UARD
(trademark of Monsanto Comp., USA) are placed into each pot. After 2 days, the appropriate test
insects are placed into the treated soil. After a further 7 days, the efficacy of the active compound
is determined by countin the corn plants that have emered ( plant = 20% activity).
Example I
Heliothis virescens test - treatment of transenic plants
Solvent: 7 parts by weiht of acetone
Emulsifier: part by weiht of alkylaryl polylycol ether
To produce a suitable preparation of active compound, part by weiht of active compound is
mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate diluted with water to the desired concentration.
Soybean shoots (lycine max) of the cultivar Roundup Ready (trademark of Monsanto Comp.
USA) are treated by bein dipped into the preparation of active compound of the desired
concentration and are populated with the tobacco budworm Heliothis virescens while the leaves
are still moist.
After the desired period of time, the k i l l of the insects is determined.

Claims
A compound of the fomula (1)
(Figure Removed)in whichepesents iodine,X epesents hydogen, alkyl, halogen, haloalkyl, alkoxy o haloalkoxy,Y epesents hydogen, alkyl, halogen o alkoxy,
with the poviso that at least one of the adicals 2, X o Y is located in the 2-position of the
phenyl adical and is not hydogen,CKE epesents one of the goupsepesents hydogen, in each case optionally halogen-substituted alkyl,alkenyl, alkoxyalkyl, alkylthioalkyl, satuated o unsatuated, optionallysubstituted cycloalkyl in which optionally at least one ing atom is
eplaced by a heteoatom, o in each case optionally halogen-, alkyl-,haloalkyl-, alkoxy-, haloalkoxy-, cyano- o nito-substituted ayl, aylalkylo hetayl,epesents hydogen, alkyl o alkoxyalkyl, oA and B togethe with the cabon atom to which they ae attached epesent a
satuated o unsatuated, unsubstituted o substituted cycle whichoptionally contains at least one heteoatom,D epesents hydogen o an optionally substituted adical fom the goup
consisting of alkyl, alkenyl, alkynyl, alkoxyalkyl, satuated o unsatuated
cycloalkyl in which optionally one o moe ing membes ae eplaced by
heteoatoms, aylalkyl, ayl,i hetaylalkyl o hetayl o
A and D togethe with the atoms to which they ae attached epesent a satuated
o unsatuated cycle which is unsubstituted o substituted in the A,D
moiety and optionally contains at least one (in the case of CKE=g one
futhe) heteoatom, o
A and ' togethe epesent alkanediyl o alkenediyl, optionally substituted by
hydoxyl, in each case optionally substituted alkyl, alkoxy, alkylthio,
cycloalkyl, benzyloxy o ayl o
epesents hydogen o alkyl,
epesents hydogen, epesents optionally substituted alkyl, alkoxyalkyl,
alkylthioalkyl, optionally substituted cycloalkyl (in which optionally one
methylene goup is eplaced by oxygen o sulfu) o optionally substituted
phenyl, otogethe with the cabon atom to which they ae attached epesent a
satuated o unsatuated, unsubstituted o substituted cycle which
optionally contains a heteoatom,
g epesents hydogen (a) o epesents one of the goups
(Figure Removed)
E epesents a metal ion euivalent o an ammonium ion,
L epesents oxygen o sulfu,
M epesents oxygen o sulfu,
' epesents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl o optionally halogen-,
alkyl- o alkoxy-substituted cycloalkyl which may be inteupted by at
least one heteoatom, in each case optionally substituted phenyl,
phenylalkyl, hetayl, phenoxyalkyl o hetayloxyalkyl,
2 epesents in each case optionally halogen-substituted alkyl, alkenyl,
alkoxyalkyl, polyalkoxyalkyl o epesents in each case optionally
substituted cycloalkyl, phenyl o benzyl,
, and - independently of one anothe epesent in each case optionally
halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino,
alkylthio, alkenylthio, cycloalkylthio o epesent in each case
optionally substituted phenyl, benzyl, phenoxy o phenylthio,
.6 and 7 independently of one anothe epesent hydogen, in each case
optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy,
alkoxyalkyl, epesent optionally substituted phenyl, epesent
optionally substituted benzyl, o togethe with the N atom to which
they ae attached epesent a cycle which is optionally inteupted by
oxygen o sulfu.
2. The compound of the fomula (1) as claimed in claim i in which
epesents iodine,
with the poviso that at least one of the adicals 2, X o Y is located in the 2-position of the
phenyl adical and is not hydogen,
CKE epesents one of the goups
(Figure Removed)
A epesents hydogen o in each case optionally halogen-substituted C
B epesents hydogen, A, B and the cabon atom to which they ae attached epesent satuated o unsatuated in which optionally one ing membe
is eplaced by oxygen o sulfu and which ae optionally mono- o disubstituted by
alkylthio, halogen o phenyl o
A, B and the cabon atom to which they ae attached epesent -cycloalky! which
is substituted by an alkylenedithiol goup o by an alkylenedioxyl goup o by an
alkylenediyl goup which optionally contains one o two not diectly ad2acent
oxygen and/o sulfu atoms and which is optionally substituted by -alkyl,
which goup, togethe with the cabon atom to which it is attached, foms a futhe
five- to eight-membeed ing, o
A, B and the cabon atom to which they ae attached in which two substituents togethe with the cabon atoms to
which they ae attached epesent in each case optionally o halogen- in which optionally one methylene goup is eplaced by oxygen o
D epesents hydogen, in each case optionally halogen-substituted C
which optionally one ing membe is eplaced by oxygen o sulfu o in each case
cyano- o nito-substituted phenyl, hetayl having 5 o 6 ing atoms,
phenyl--alkyl o hetayl- -alkyl having 5 o 6 ing atoms o
A and D togethe epesent in each case optionally substituted C3-C5-alkanediyl o C3-C6-
alkenediyl in which optionally one methylene goup is eplaced by a cabonyl
goup, oxygen o sulfu,
possible substituents being in each case:
halogen, hydoxyl, mecapto o in each case optionally halogen-substituted C\-
benzyloxy, o a futhe C3-Cg-alkanediyl gouping, C3-C6-alkenediyl gouping o
a butadienyl gouping which is optionally substituted by -alkyl o in which
optionally two ad2acent substituents togethe with the cabon atoms to which they
ae attached fom a futhe satuated o unsatuated cycle having 5 o 6 ing atoms
(in the case of the compound of the fomula (i-i) A and D in this case togethe
with the atoms to which they ae attached epesent, fo example, the goups AD-i
to AD- 10 mentioned futhe below) that may contain oxygen o sulfu o which
optionally contains one of the following goups
(Figure Removed)
A and ' togethe epesent C3-C5-alkanediyl o C4-C3-alkenediyl, each of which is
optionally mono- o disubstituted by identical o diffeent substituents fom the
goup consisting of halogen; hydoxylC3-C7-cycloalkyl, each of which is optionally mono- to tisubstituted byidentical o diffeent halogen substituents; and benzyloxy o phenyl, each of which
is optionally mono- to tisubstituted by identical o diffeent substituents fom the
goup consisting of halogen, o CC-alkenediyl futhemoe optionally contains one of the goups
below
(Figure Removed)
E epesents a metal ion euivalent o an ammonium ion,
L epesents oxygen o sulfu and
M epesents oxygen o sulfu.
optionally one cabon atom is eplaced by oxygen o sulfu,
epesents hydogen, epesents in each case optionally halogen-substituted
and a independently of one anothe epesent hydogen, epesent optionally
halogen-substituted
and a togethe with the cabon atom to which they ae attached epesent a
3. The compound of the fomula (1) as claimed in claim i in which
2 epesents iodine,
X epesents hydogen, fluoine, chloine, bomine, iodine,
Y epesents hydogen, fluoine, chloine, bomine, iodine,
with the poviso that at least one of the adicals 2, X o Y is located in the 2-position of the
phenyl adical and is not hydogen,
A epesents hydogen, epesents of which is optionally mono- to tisubstituted by fluoine o chloine, epesents
-cycloalkyl which is optionally mono- to disubstituted by C2-C2-alkoxy o (but not in the case of the compounds of the fomulae (i-3), (i-4),
(i-6) and (i-7)) epesents phenyl o benzyl, each of which is optionally mono- to
disubstituted by fluoine, chloine, bomine, C4-alkoxy, C1C2-haloalkoxy, cyano o nito,
B epesents hydogen, C2-Calkyl o CpCa-alkoxy-CpC2-alkyl, o
A, B and the cabon atom to which they ae attached epesent satuated o unsatuated
C5-C7-cycloalkyl in which optionally one ing membe is eplaced by oxygen o
sulfu and which is optionally mono- to disubstituted by tifluoomethyl, C2-Cg-alkoxy o C2-alkoxy-C2-alkoxy, with the poviso
that in this paticulaly pefeably epesents hydogen o methyl, o
A, B and the cabon atom to which they ae attached epesent C5-C6-cycloalkyl which
is substituted by an alkylenedithiol goup o by an alkylenedioxyl goup o by an
alkylenediyl goup which optionally contains one o two not diectly ad2acent
oxygen o sulfu atoms and which is optionally substituted by methyl o ethyl,
which goup togethe with the cabon atom to which it is attached foms a futhe
five- o six-membeed ing, with the poviso that in this case paticulaly
pefeably epesents hydogen o methyl,
A, B and the cabon atom to which they ae attached epesent C3-Cg-cycloalkyl o 05-
Cg-cycloalkenyl in which two substituents togethe with the cabon atoms to
which they ae attached epesent in each case optionally C2-C2-alkyl- o C2-C2-
alkoxy-substituted C2-C4-alkanediyl, C2-C4-alkenediyl o butadienediyl, with the
poviso that in this case epesents hydogen o methyl,
D epesents hydogen, epesents C2-Cg-alkyl, C3-C6-alkenyl, C2-C4-alkoxy-C2-
C3-alkyl, each of which is optionally mono- to tisubstituted by fluoine,
epesents C3-Cg-cycloalkyl which is optionally mono- to disubstituted by C\-C-
alkyl, C2-C4-alkoxy o -haloalkyl and in which optionally one methylene
goup is eplaced by oxygen o (but not in the case of the compounds of the
fomulae (i-l)) epesents phenyl o pyidyl, each of which is optionally mono- to
disubstituted by fluoine, chloine, bomine, C1-C4-alkyl, C2-C4-haloalkyl, C2-
C4-alkoxy o C|-C4-haloaikoxy, o
A and D togethe epesent optionally mono- to disubstituted C3-C5-alkanediyl in which
one methylene goup may be eplaced by a cabonyl goup (but not in the case of
the compounds of the fomula (i-l)), oxygen o sulfu, possible substituents being
C1-C2-alkyl o C1-C2-alkoxy, o
A and D (in the case of the compounds of the fomula (i-l)) togethe with the atoms to
which they ae attached epesent one of the goups AD-i to AD-10:
A and togethe epesent C3-C4alkanediyl which is optionally mono- o disubstituted
by identical o diffeent substituents selected fom the goup consisting of C-C2-
alkyl and C2-C2-alkoxy, o
! epesents hydogen,
2 epesents hydogen,
% C and " independently of one anothe epesent hydogen o C2-C2-alkyl,
epesents hydogen, C1-C4-alkyl, o C3-C6-cycloalkyl which is optionally monoto
disubstituted by methyl o methoxy, o
-3 and togethe with the cabon to which they ae attached epesent an optionally C2-
C2-alkyl- o C1-C2-aikoxy-substituted satuated C5-Cg-ing in which optionally
one ing membe is eplaced by oxygen o sulfu, with the poviso that in this case
A epesents hydogen o methyl,
g epesents hydogen (a) o epesents one of the goups
E epesents a metal ion euivalent o an ammonium ion,
L epesents oxygen o sulfu and
M epesents oxygen o sulfu,
i epesents C2-Cg-alkyl, C2-C1g-alkenyl, C \ -C4-alkoxy-C 2 -C2-alkyl, C2-C
alkylthio-C2-C2-alkyl, each of which is optionally mono- to tisubstituted by
fluoine o chloine, o C3-C6-cycloalkyl which is optionally mono- to
disubstituted by fluoine, chloine, C1-C2-alkyl o C1-C2-alkoxy and in which
optionally one o two not diectly ad2acent ing membes ae eplaced by oxygen,
epesents phenyl which is optionally mono- to disubstituted by fluoine, chloine,
bomine, cyano, nito, C1-C4-alkyl, C2-Calkoxy, C1-C2-haloalkyl o C2
haloalkoxy,
2 epesents C2-Cg-alkyl, C-Cg-alkenyl o C1-C4-alkoxy-C2-C4-alkyl, each of
which is optionally mono- to tisubstituted by fluoine,
epesents C3-Cg-cycloalkyl which is optionally monosubstituted by C2-C2-aikyl
o C1-C2-alkoxy o
epesents phenyl o benzyl, each of which is optionally mono- to disubstituted by
fluoine, chloine, bomine, cyano, nito, C2-C4-alkyl, C2-C3-alkoxy,
tifluoomethyl o tifluoomethoxy,
- epesents C2-C-alkyl which is optionally mono- to tisubstituted by fluoine o
epesents phenyl which is optionally monosubstituted by fluoine, chloine,
bomine, C2-C/2-alkyl, C1-g4-alkoxy, tifluoomethyl, tifluoomethoxy, cyano o
nito,
epesents C1-C5-alkyl, C2-Cg-alkoxy, C2-Cg-alkylamino, dKC2-Cg-alkyOamino,
C1-C6-alkylthio, C3-C4-alkenylthio, C3-C6-cycloalkylthio o epesents phenyl,
phenoxy o phenylthio, each of which is optionally monosubstituted by fluoine,
chloine, bomine, nito, cyano, C1-C3-alkoxy, C1-C3-haloalkoxy, C2-C3-
alkylthio, C1-C3-haioalkylthio, C2-C3-alkyl o tifluoomethyl,
epesents C i -C6-alkoxy o C i -C6-alkylthio,
epesents hydogen, C2-Cg-alkyl, C3-Cg-cycloalkyl, C i -Cg-alkoxy, C1-C6-alkoxy-C1-C4-alky1 epesents phenyl which is optionally
monosubstituted by fluoine, chloine, bomine, tifluoomethyl, C2-C4-alkyl o
C2-C4-alkoxy, epesents benzyl which is optionally monosubstituted by fluoine,
chloine, bomine, C1-C4-alkyl, tifluoomethyl o C 2 -C4-aikoxy,
epesents C|-C6-alkyl, C.C6-alkenyl o C|-C6-alkoxy-C1-C4-alkyl,
and togethe epesent an optionally methyl- o ethyl-substituted C4-C5-alkylene
adical in which optionally one methylene goup is eplaced by oxygen o sulfu.
4. The compound of the fomula (1) as claimed in claim i in which
2 epesents iodine,
X epesents hydogen, fluoine, chloine, bomine, methyl, ethyl, popyl, methoxy o
ethoxy,
Y epesents hydogen, chloine, bomine, methyl, ethyl, popyl o methoxy,
with the poviso that at least one of the adicals 2, X o Y is located in the 2-position of the
phenyl adical and is not hydogen,
CKE epesents one of the goups
A epesents hydogen, epesents C2-Calkyl o C1-C2-alkoxy-C1-C2-alkyl, each
of which is optionally mono- to tisubstituted by fluoine, epesents cyclopopyl,
cyclopentyl o cyclohexyl and, only in the case of the compounds of the fomula
(i-5), epesents phenyl which is optionally mono- to disubstituted by fluoine,
chloine, bomine, methyl, ethyl, n-popyl, isopopyl, methoxy, ethoxy,
tifluoomethyl, tifluoomethoxy, cyano o nito,
B epesents hydogen, methyl o ethyl, o
A, B and the cabon atom to which they ae attached epesent satuated C$-Cficycloalkyl
in which optionally one ing membe is eplaced by oxygen o sulfu
and which is optionally monosubstituted by methyl, ethyl, popyl, isopopyl,
tifluoomethyl, methoxy, ethoxy, popoxy, methoxyethoxy, butoxy o
ethoxyethoxy, with the poviso that in this case C epesents hydogen, o
A, B and the cabon atom to which they ae attached epesent Cg-cycloalkyl which is
optionally substituted by an alkylenedioxyl goup which contains two not diectly
ad2acent oxygen atoms, with the poviso that in this case vey paticulaly
pefeably epesents hydogen, o
A, B and the cabon atom to which they ae attached epesent C5-Cg-cycloalkyl o 05-
C-cycloalkenyl in which two substituents togethe with the cabon atoms to
which they ae attached epesent C2-C4-alkanediyl o C2-C4-alkenediyl o
butadienediyl, with the poviso that in this case - epesents hydogen,
D epesents hydogen, epesents C1-C4-alkyl, C3-C4-alkenyl, C2-C4-alkoxy-C2-
C3-alkyl, each of which is optionally mono- to tisubstituted by fluoine,
epesents cyclopopyl, cyclopentyl o cyclohexyl o (but not in the case of the
compounds of the fomulae (i-i)) epesents phenyl o pyidyl, each of which is
optionally monosubstituted by fluoine, chloine, methyl, ethyl, n-popyl,
isopopyl, methoxy, ethoxy o tifluoomethyl,
o
A and D togethe epesent C3-C5-alkanediyl which is optionally monosubstituted by
methyl o methoxy and in which optionally one cabon atom is eplaced by oxygen
o sulfu o epesent the goup AD-1
A and ' togethe epesent C3-C4-alkanediyl which is optionally mono- o disubstituted
by methyl o methoxy, o
! epesents hydogen,
epesents hydogen,
and independently of one anothe epesent hydogen o methyl,
epesents hydogen, methyl, ethyl o popyl, o
and togethe with the cabon to which they ae attached epesent a satuated €5-
C6-ing which is optionally monosubstituted by methyl o methoxy, with the
poviso that in this case A epesents hydogen,
g epesents hydogen (a) o epesents one of the goups
L epesents oxygen o sulfu,
M epesents oxygen o sulfu and
E epesents an ammonium ion,
i epesents C2-Cg-alkyl, C2-C17-alkenyl, C2-alkoxy-C2-alkyl, C1-C2-
alkylthio-C1-alkyl, each of which is optionally monosubstituted by chloine, o
epesents cyclopopyl o cyclohexyl, each of which is optionally monosubstituted
by fluoine, chloine, methyl o methoxy,
epesents phenyl which is optionally monosubstituted by fluoine, chloine,
bomine, cyano, nito, methyl, methoxy, tifluoomethyl o tifluoomethoxy,
.2 epesents C1-Cg-alkyl, C2C6-alkenyl o C2-C4-alkoxy-C2-C3-alkyl, each of
which is optionally monosubstituted by fluoine, o epesents phenyl o ben2yl,
3 epesents C|-Cg-alkyi.
5. The compound of the fomula (1) as claimed in claim i in which
2 epesents iodine,
X epesents hydogen, chloine, methyl o ethyl,
Y epesents hydogen, chloine, methyl o ethyl,
with the poviso that at least one of the adicals 2, X o Y is located in the 2-position of the
phenyl adical and is not hydogen,
whee the adicals 2, X and Y with thei meanings ae aanged in the following phenyl
substitution pattens
epesents C|-Chalky i o cyclopopyl,
epesents hydogen o methyl,
A, B and the cabon atom to which they ae attached epesent satuated Csin
which optionally one ing membe is eplaced by oxygen and which is
optionally monosubstituted by methyl, methoxy o popoxy,
A and D epesent the goup AD-1
in the case of CKE = goup (g) A and D togethe epesent C3-C5-alkanediyl,
g epesents hydogen (a) o epesents one of the goups
.i epesents C|-C6-alkyl, CC2-alkoxy-C|-alkyl, cyclopopyl, each of which is
optionally monosubstituted by chloine, o epesents phenyl which is optionally
monosubstituted by chloine,
.2 epesents C2-Cg-alkyl C2-Cg-alkenyl o benzyl.
A pocess fo pepaing compounds of the fomula (1) as claimed in claim 1 wheein, to
obtain
(Figue Removed)
epesents alkyl
ae condensed intamoleculaly in the pesence of a diluent and in the pesence of a base,
(B) compounds of the fomula (i-2-a)
(Figue Removed)A, B, 2, X , Y and ae as defined above
ae condensed intamoleculaly in the pesence of a diluent and in the pesence of a base,
(C) compounds of the fomula (i-3-a)
in which
A, B, 2, X and Y ae as defined above,
compounds of the fomula (iV)
A, B, 2, X, Y and % ae as defined above and
V epesents hydogen, halogen, alkyl o alkoxy,
ae cyclized intamoleculaly, if appopiate in the pesence of a diluent and in the
pesence of an aC1d,
(D) compounds of the fomula (i-4-a)
2, X and Y ae as defined above and
Hal epesents halogen,
if appopiate in the pesence of a diluent and if appopiate in the pesence of an aC1d
accepto,
(E) compounds of the fomula (i-5-a)
A, 2, X and Y ae as defined above,
compounds of the fomula (Vii)
in which
A is as defined above
ae eacted with compounds of the fomula (Vi)
Hal, 2, X and Y ae as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of an aC1d
accepto,
(F) compounds of the fomula (i-6-a)
in which
A, B, l, , 2, X and Y ae as defined above and
° epesents alkyl
ae cyclized intamoleculaly, if appopiate in the pesence of a diluent and in the
pesence of a base,
(g) compounds of the fomula (i-7-a)
A, B, 2, 3, 4, 5, 6, X and Y ae as defined above,
compounds of the fomula (iX)
A, B, 2, 3, 4, 5, 6, X and Y ae as defined above
and
° epsents alkyl
ae condensed intamoleC1ilaly in the pesence of a diluent and in the pesence of a base,
(H) compounds of the fomula (i-g-a)
A, D, 2, X and Y ae as defined above,
compounds of the fomula (X)
A and D ae as defined above
a) ae eacted with compounds of the fomula (Vi)
(Figue Removed)
Hal, X, Y and 2 ae as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of an aC1d accepto,
B) ae eacted with compounds of the fomula (Xi)
2, X and Y ae as defined above
and U epesents NH2 o O-g, whee g is as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of a base, o
y) ae eacted with compounds of the fomula (Xii)
A, D, 2, X, Y and ae as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of a base,
(1) compounds of the fomulae (i-!-b) to (i-g-b) shown above in which A, B, D, 2, ,
2, 3, O4, 5, 6, 1 X, and Y ae as defined above, compounds of the
fomulae (i-i-a) to (i-g-a) shown above in which A, B, D, 2, 1 2, 3, 4, 5,
", X and Y ae as defined above ae in each case
(a) eacted with aC1d halides of the fomula (Xiii)
(B) eacted with caboxylic anhydides of the fomula (XiV)
'-CO-O-CO-i (XiV)
in which
! is as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of an aC1d
binde,
(2) compounds of the fomulae (i-l-c) to (i-g-c) shown above in which A, B, D, 2, ,
2, 3, O4, 5, 6, 2, M, X and Y ae as defined above and L epesents
oxygen, compounds of the fomulae (i-l-a) to (i-g-a) shown above in which A, B,
D, 2, l, 2, 3, 4, 5, 6? x and Y ae as defined above ae in each case
eacted with chloofomic estes o chloofomic thioestes of the fomula (XV)
2-M-CO-C1 (XV)
in which
2 and M ae as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of an aC1d
binde,
(K) compounds of the fomulae (i-l-c) to (i-g-c) shown above in which A, B, D, 2, ,
2, 3, 4, 5, 6, 2, M, X and Y ae as defined above and L epesents sulfu,
compounds of the fomulae (i-l-a) to (i-g-a) shown above in which A, B, D, 2, ,
2, O3, O4. , , X and Y ae as defined above ae in each case
eacted with chloomonothiofomic estes o chloodithiofomic estes of the
fomula (XVi)
M and 2 ae as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of an aC1d
binde,
(L) compounds of the fomulae (i-l-d) to (i-g-d) shown above in which A, B, D, 2, ,
2, 3, 4, 5, 6, 3, X and Y ae as defined above, compounds of the
fomulae (i-l-a) to (i-g-a) shown above in which A, B, D, 2, 1 2, 3, 4, 5,
, X and Y ae as defined above ae in each case
eacted with sulfonyl chloides of the fomula (XVii)
(Figue Removed)
is as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of an aC1d
binde,
(M) compounds of the fomulae (i-l-e) to (i-g-e) shown above in which A, B, D, 2, L,
1 2, 3, 4, 5, 6, 4, 5, X and Y ae as defined above, compounds of the
fomulae (i-l-a) to (i-g-a) shown above in which A, B, D, 2, 1 2, 3, 4, 5,
", X and Y ae as defined above ae in each case
eacted with phosphous compounds of the fomula (XViii)
L, 4 and ae as defined above and
Hal epesents halogen,
if appopiate in the pesence of a diluent and if appopiate in the pesence of an aC1d
binde,
(N) compounds of the fomulae (i-l-f) to (i-g-f) shown above in which A, B, D, E, 2,
, 2, 3, 4, , 6, x and Y ae as defined above, compounds of the
fomulae (i-l-a) to (i-g-a) in which A, B, D, 2, 1 2, 3, 4, 5, 6, X and Y
ae as defined above ae in each case
eacted with metal compounds o amines of the fomulae (XiX) o (XX)
t epesents the numbe i o 2 and
.10, ! ', '2 independently of one anothe epesent hydogen o alkyl,
if appopiate in the pesence of a diluent,
compounds of the fomulae (i-l-g) to (i-g-g) shown above in which A, B, D, 2, L,
1 2, 3, 4, 5, 6, 6, 7 X and Y ae as defined above, compounds of the
fomulae (i-l-a) to (i-g-a) shown above in which A, B, D, 2, 1 2, 3, 4, 5,
, X and Y ae as defined above ae in each case
(a) eacted with isocyanates o isothiocyanates of the fomula (XXi)
.6 and L ae as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of a catalyst,
o
(6) eacted with cabamoyl chloides o thiocabamoyl chloides of the fomula (XXii)
L, .6 and 7 ae as defined above,
if appopiate in the pesence of a diluent and if appopiate in the pesence of an aC1d
binde,compounds of the fomulae (i-i-a) to i-g-a) shown above in which A, B, D, 2, 1
2, 3, 4, 5, 6, X and Y ae as defined above, compounds of the fomulae (i-i-
a') to (i-g-ai) in which A, B, D, 1 2, 3, 4, 5, 6, X and Y ae as defined
above and W epesents bomine
a) ae eacted with metal iodides, if appopiate in the pesence of a diluent, a Cu(1)
salt and a base, o
B) ae sub2ected to a halogen/metal exchange with metal oganyls and the anion
fomed is uenched with iodinating agents.
7. The use of compounds of the fomula (1) as claimed in claim i fo pepaing pestiC1des
and/o hebiC1des.
g. A pestiC1de and/o hebiC1de which compises at least one compound of the fomula (1) as
claimed in claim i.
9. A method fo contolling animal pests and/o unwanted vegetation which compises
allowing compounds of the fomula (1) as claimed in claim i to act on pests and/o thei
habitats.
10. The use of compounds of the fomula (1) as claimed in claim i fo contolling animal pests
and/o unwanted vegetation.
ii. A pocess fo pepaing pestiC1des and/o hebiC1des which compises mixing compounds
of the fomula (1) as claimed in claim i with extendes and/o sufactants.
i2. A composition compising an effective amount of an active compound combination
compising, as components,
(ai) at least one substituted cyclic ketoenol of the fomula (1) in which CKE, 2, X and Y
ae as defined above
and
(bi) at least one cop plant compatibility-impoving compound fom the following goup
of compounds:
4-dichlooacetyl-l-oxa-4-azaspio[4.5idecane (AD-67, MON-4660), i-dichlooacetylhexahydo-
3,3,ga-timethylpyplo[l,2-aipyimidin-6(2H)-one (dicyclonon, BAS-145i3g),
4-dichlooacetyl-3,4-dihydo-3-methyl-2H-l,4-benzoxazine (benoxaco), i -methylhexyl
5-chloouinoline-g-oxyacetate (clouintocet-mexyl - cf. also elated compounds in
EP-A-g6750, EP-A-94349, EP-A-i9i736, EP-A-492366), 3-(2-chloobenzyi)-l-(l-methyll-
phenylethyl)uea (cumyluon), a-(cyanomethoximino)phenylacetonitile (cyometinil),
2,4-dichloophenoxyacetic aC1d (2,4-D), 4-(2,4-dichloophenoxy)butyic aC1d (2,4-DB),
i-(i-methyl-l-phenylethyl)-3-(4-methylphenyl)uea (daimuon, dymon), 3,6-dichloo-
2-methoxybenzoic aC1d (dicamba), S-l-methyl-i-phenylethyl pipeidine-i-thiocaboxylate
(dimepipeate), 2,2-dichloo-N-(2-oxo-2-(2-popenylamino)ethyl)-N-(2-popenyl)-
acetamide (DKA-24), 2,2-dichloo-N,N-di-2-popenylacetamide (dichlomid),
4,6-dichloo-2-phenylpyimidine (fencloim), ethyl l-(2,4-dichloophenyl)-5-
tichloomethyl-lH-l,2,4-tiazole-3-caboxylate (fenchloazole-ethyl - cf. also elated
compounds in EP-A-i74562 and EP-A-346620), phenylmethyl 2-chloo-4-
tifluoomethylthiazole-5-caboxylate (fluazole), 4-chloo-N-(l,3-dioxolan-2-ylmethoxy)-
a-tifluooacetophenone oxime (fluxofenim), 3-dichlooacetyl-5-(2-fuanyl)-2,2-
dimethyloxazolidine (fuilazole, MON-i3900), ethyl 4,5-dihydo-5,5-diphenyl-3-
isoxazolecaboxylate (isoxadifen-ethyl - cf. also elated compounds in WO-A-95/07g97),
l-(ethoxycabonyl)ethyl 3,6-dichioo-2-methoxybenzoate (lactidichlo), (4-chloo-otolyloxy)
acetic aC1d (MCPA), 2-(4-chloo-o-tolyloxy)popionic aC1d (mecopop), diethyl i-
(2,4-dichoophenyl)-4,5-dihydo-5-methyl-lH-pyazoie-3,5-dicaboxyiate (mefenpydiethyl
- cf. also elated compounds in WO-A-9i/07g74), 2-dichloomethyl-2-methyl-13-
dioxolane (Mg-i9i), 2-popenyl-l-oxa-4-azaspio[4.5idecane-4-cabodithioate (Mg-g3g),
1g-naphthalic anhydide, a-(l,3-dioxolan-2-ylmethoximino)phenylacetonitile
(oxabetinil), 2,2-dichloo-N-( 13-dioxolan-2-ylmethyl)-N-(2-popenyl)acetamide
(PPg-i292), 3-dichlooacetyl-2,2-dimethyloxazolidine (-2g725), 3-dichlooacetyl-
2,2,5-timethyloxazolidine (-2914g), 4-(4-chloo-o-tolyl)butyic aC1d, 4-(4-chloophenoxy)
butyic aC1d, diphenylmethoxyacetic aC1d, methyl diphenylmethoxyacetate, ethyl
diphenylmethoxyacetate, methyl l-(2-chloophenyl)-5-phenyl-lH-pyazole-3-caboxylate,
ethyl l-(2,4-dichloophenyl)-5-methyl-lH-pyazole-3-caboxylate, ethyl l-(2,4-dichloophenyl)-
5-isopopyl-l H-pyazole-3-caboxylate, ethyl l-(2,4-dichloophenyl)-5-(l,l-di-
233-
methylethyl)-! H-pyazole-3-caboxylate, ethyl l-(2,4-dichloophenyl)-5-phenyllH-
pyazole-3-caboxylate (cf. also elated compounds in EP-A-269g06 and
EP-A-333i3i), ethyl 5-(2,4-dichloobenzyl)-2-isoxazoline-3-caboxylate, ethyl 5-phenyl-
2-isoxazoline-3-caboxylate, ethyl 5-(4-fiuoophenyl)-5-phenyl-2-isoxazoline-
3-caboxylate (cf. also elated compounds in WO-A-9i/0g202), 13-dimethylbut-l-yl
5-chloouinoline-g-oxyacetate, 4-allyloxybutyl 5-chloouinoline-g-oxyacetate,
l-allyloxypop-2-yl 5-chloouinoline-g-oxyacetate, methyl 5-chloouinoxaline-g-oxyacetate,
ethyl 5-chloouinoline-g-oxyacetate, allyl 5-chloouinoxaline-g-oxyacetate,
2-oxopop-l-yi 5-chloouinoline-g-oxyacetate, diethyl 5-chloouinoline-g-oxymalonate,
diallyl 5-chloouinoxaline-g-oxymalonate, diethyl 5-chloouinoline-g-oxymalonate (cf.
also elated compounds in EP-A-5g2i9g), 4-caboxychoman-4-ylacetic aC1d (AC-3044i5,
cf. EP-A-6i36ig), 4-chloophenoxyacetic aC1d, 3,3'-dimethyl-4-methoxybenzophenone,
l-bomo-4-chioomethyisulfonylbenzene, l-[4-(N-2-methoxybenzoylsulfamoyl)phenyli-3-
methyluea (also known as N-(2-methoxybenzoyl)-4-[(methylaminocabonyl)-
aminoibenzenesulfonamide), l-[4-(N-2-methoxybenzoyisulfamoyl)phenyli-3,3-dimethyluea,
l-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyli-3-methyluea,
l-[4-(N-naphthylsuifamoyl)phenyli-3,3-dimethyluea, N-(2-methoxy-5-methylbenzoyl)-4-
(cyclopopylaminocabonyl)benzenesulfonamide,
and/o one of the following compounds, defined by geneal fomulae,
of the geneal fomula (i la)
(Figue Removed)
m epesents a numbe 0, 1 2, 3, 4 o 5,
Ai epesents one of the divalent heteocyclic goupings shown below
n epesents a numbe 0, 1 2, 3, 4 o 5,
A2 epesents optionally CC4-alkyi- and/o C1-C4-alkoxy-cabonyl- and/o CpC4-
alkenyloxy-cabonyl-substituted alkanediyl having i o 2 cabon atoms,
14 epesents hydoxyl, mecapto, amino, CpCe-alkoxy, C1-Ce-alkylthio, -Cealkylamino
o di(C|-C4-aikyl)-amino,
i5 epesents hydoxyl, mecapto, amino, CC7-alkoxy, CC6-alkenyloxy, C\-C&-
alkenyloxy-C|-Cfi-alkoxy, CC6-alkylthio, C|-C6-alkylamino o di(C1-C4-alkyl)-
amino,
i6 epesents in each case optionally fluoine-, chloine- and/o bomine-substituted C
C4-alkyl,
epesents hydogen, in each case optionally fluoine-, chloine- and/o bominesubstituted
C,-C6-alkyl, C2-C6-alkenyl o C2-C6-alkynyl, C1-C4-alkoxy-C,-C4-alkyl,
dioxolanyl-CC4-alkyl, fuyl, fuyl-C1-C4-alkyl, thienyl, thiazolyl, pipeidinyl, o
optionally fluoine-, chloine- and/o bomine- o C1-C4-aikyl-substituted phenyl,
epesents hydogen, in each case optionally fluoine-, chloine- and/o bominesubstituted
C|-C()-alkyl, C2-C6-alkenyl o C2-C6-alkynyl, C1-C4-alkoxy-CC4-alkyl,
dioxolanyl-C|-Calkyl, fuyl, fuyl-CC4-alkyl, thienyl, thiazolyl, pipeidinyl, o
optionally fluoine-, chloine- and/o bomine- o Cp-alkyl-substituted phenyl,
i7 and ig also togethe epesent C3-C6-alkanediyl o C2-C5-oxaalkanediyl, each of which is
optionally substituted by CC4-alkyl, phenyl, fuyl, a fused benzene ing o by two
substituents which, togethe with the C atom to which they ae attached, fom a 5- o
6-membeed cabocycle,
i9 epesents hydogen, cyano, halogen, o epesents in each case optionally fluoine-,
chloine- and/o bomine-substituted C1-C4-alkyl, C3-C6-cycloalkyl o phenyl,
20 epesents hydogen, in each case optionally hydoxyl-, cyano-, halogen- o CC4-
alkoxy-substituted CC6-aikyl, C3-C6-cycloalkyi oti-(CC4-alkyl)-siiyl,
2i epesents hydogen, cyano, halogen, o epesents in each case optionally fluoine-,
chloine- and/o bomine-substituted C|-C4-alkyl, C3-C6-cycloalkyl o phenyl,
Xi epesents nito, cyano, halogen, C|-C4-alkyl, CC4-haloalkyl, CC4-alkoxy o
CC4-haloalkoxy,
X2 epesents hydogen, cyano, nito, halogen, C,-C4-alkyl, C|-C4-haloalkyl, C1-C4-
alkoxy o CChaloalkoxy,
X3 epesents hydogen, cyano, nito, halogen, CC4-alkyl, C,-C4-haloalkyl, CC4-
alkoxy o C|-C4-haloalkoxy,
and/o the following compounds, defined by geneal fomulae,
of the geneal fomula (lid)
t epesents a numbe 0, 1 2, 3, 4 o 5,
v epesents a numbe 0, 12,3,4 o 5,
22 epesents hydogen o CC4-alkyl,
23 epesents hydogen o CC4-alkyl,
24 epesents hydogen, in each case optionally cyano-, halogen- o CpC4-alkoxysubstituted
CC6-alkyl, CC6-alkoxy, CC6-alkyithio, C1-C6-alkylamino o di(C,-C4-
alkyl)-amino, o in each case optionally cyano-, halogen- o C1-C4-alkyl-substituted
C3-C6-cycloalkyl, gC6-cycloaikyioxy, C3-C6-cycloaikylthio o C3-Cecycloalkylamino,
25 epesents hydogen, optionally cyano-, hydoxyl-, halogen- o C1-C4-alkoxysubstituted
C|-C()-alkyl, in each case optionally cyano- o halogen-substituted C3-C6-
alkenyl o C3-,-alkynyl, o optionally cyano-, halogen- o C|-C4-alkyl-substituted
C2-Ce-cycloalkyl,
25 epesents hydogen, optionally cyano-, hydoxyl-, halogen- o CC4-alkoxysubstituted
C1-C6-alkyl, in each case optionally cyano- o halogen-substituted C3-C6-
alkenyl o C3-C6-aikynyl, optionally cyano-, halogen- o C1-C4-alkyl-substituted
C3-C6-cycloalkyl, o optionally nito-, cyano-, halogen-, CC4-alkyl-, CC4-haloalkyl-,
C1-C4-aikoxy- o CC4-haloalkoxy-substituted phenyl, o togethe with 25
epesents in each case optionally C|-C4-alkyl-substituted C2-C6-alkanediyl o C2-C$-
oxaalkanediyl,
X4 epesents nito, cyano, caboxyl, cabamoyl, fomyl, sulfamoyl, hydoxyl, amino,
halogen, C|-C4-alkyl, CC4-haloalkyl, C,-C4-alkoxy o C1-C4-haioalkoxy, and
X5 epesents nito, cyano. caboxyl, cabamoyl, fomyl, sulfamoyl, hydoxyl, amino,
halogen, CC4-alkyl, CC4-haloalkyl, CC4-alkoxy o d-C4-haloalkoxy.
i3. The composition as claimed in claim i2 in which the cop plant compatibility-impoving
compound is selected fom the following goup of compounds:
clouintocet-mexyl, fenchloazole-ethyl, isoxadifen-ethyl, mefenpy-diethyl, fuilazole,
fencloim, cumyluon, dymon o the compounds iie-5 o iie-ii.
14. The composition as claimed in claim i2 in which the cop plant compatibility-impoving(Figue Removed)
compound is mefenpy-diethyl.
i5. A method fo contolling unwanted vegetation which compises allowing a composition as
claimed in claim i2 to act on the plants o thei habitats.
i6. The use of a composition as claimed in claim i2 fo contolling unwanted vegetation.
i7. A method fo contolling unwanted vegetation which compises allowing a compound of
the fomula (1) as claimed in claim i and a cop plant compatibility-impoving compound
as claimed in claim i2 to act, sepaately in close tempoal succession, o as a mixtue, on
the plants o thei habitats.